EP0880571A1 - Magnetisch getrennte gleichgewichtkatalysator für spezialisiertes kracken - Google Patents
Magnetisch getrennte gleichgewichtkatalysator für spezialisiertes krackenInfo
- Publication number
- EP0880571A1 EP0880571A1 EP96903789A EP96903789A EP0880571A1 EP 0880571 A1 EP0880571 A1 EP 0880571A1 EP 96903789 A EP96903789 A EP 96903789A EP 96903789 A EP96903789 A EP 96903789A EP 0880571 A1 EP0880571 A1 EP 0880571A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- feed
- catalyst
- ppm
- range
- catalytic cracking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000005336 cracking Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007885 magnetic separation Methods 0.000 claims abstract description 10
- 238000011109 contamination Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 230000005291 magnetic effect Effects 0.000 description 11
- 239000006148 magnetic separator Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 238000003339 best practice Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Definitions
- U.S. 4,591 ,425 (attorney docket 6213AUS) issued relates to the field of transferring of catalyst from a fluid catalytic cracking unit to a reduced crude catalytic cracking unit to a metals removal unit.
- U.S. 4,406,773 (attorney docket 6039AUS) relates to separation of metal contaminated cracking catalysts from a fluid catalytic cracking unit to improve activity upon recycling back to the fluid catalytic cracking unit.
- This invention relates to hydrocarbon conversions involving catalytic cracking. It also relates to magnetic separation of metal contaminated cracking catalysts such as disclosed in U.S. 4,406,773 of W. P. Hettinger, Jr. and R. M. Benslay, and U.S. 4,349,379 of Nippon Oil Company.
- hydrocarbyl feed shall mean a petroleum feedstock characterized as follows: % by weight of hydrogen in the range 6-18%; of carbon in the range 67-94%; of metal contaminates comprising nickel, cobalt, magnesium, vanadium, and sulfur in the range of 0-15%; a Conradson carbon number in the range 0-30%.
- FCC shall mean throughout this specification fluid catalytic cracking as further defmed in the Petroleum Handbook. Catalytic cracking is defined and described in Shreve's Chemical Process Industries, 5th ed., by George T. Austin, Chapter 37, pp 735-740. Catalytic cracking is also defined and described in Petroleum Refining Technology and Economics, 2nd ed., by James H. Gary and Glenn E. Handwerk, Chapter 7, pp 99-108.
- This invention arises from the discovery that instead of simply recycling magnetically separated cracking catalysts back to an FCC unit, there is a benefit in terms of activity and selectivity, in sending a portion of such magnetically separated cracking catalyst to a separate FCC unit, that is operated at different conditions from those of the FCC unit from which the separated catalyst was removed.
- this invention involves a process for the cascading of spent equilibrium catalyst from at least one first fluid catalytic cracking unit to a second fluid catalytic cracking unit. The primary difference between the first and the second unit resides in the characteristics of the hydrocarbyl feed stocks used in each.
- the characteristics of the hydrocarbyl feed in the one or more first units are: boiling range of preferably 430°F and higher with no more than 10 weight percent (wt.%) boiling above 1050°, more preferably 450°F and higher with no more than 5 wt.% boiling above 1050, and most preferably 480°F and higher with no more than 2 wt.% boiling above 1050.
- the relative characteristics of the hydrocarbyl feed in the second unit are: the second feed is higher in Ramsbottom carbon content preferably by at least 0.5, more preferably at least 1 , and most preferably at least 2, with the general range increase in Ramsbottom carbon content being about 0.5 to 4; in iron/vanadium content by a ratio preferably in the range 10: 1 to 1:10, more preferably in the range 2: 1 to 1 : 10, and most preferably in the range 1:1 to 1:10; iron/nickel content by a ratio preferably in the range 10:1 to 1:10, more prcferably by a ratio in the range 2:1 to 1 :10, and most preferably by a ratio in the range 1 : 1 to 1 : 10; and/or content of material boiling above 1050°F increased by an amount in percent by weight preferably in the range 10-70%, more preferably in the range 20-70%, and most preferably in the range 30- 70%.
- the minimum metal content of feed in the first cracker is less than 5 ppm for Ni, V, Fe, or Cu; more preferably less than 1 ppm for Ni, V, Fe, or Cu; most preferably less than .5 ppm for Ni, V, Fe, or Cu; but generally more than at least 0.4; whereas the minimum metal content of feed in the second cracker is preferably at least 3 ppm for Ni, V, Fe; more preferably at least 5 ppm for Ni, V, Fe; and most preferably at least 7 ppm for Ni, V, Fe; wherein in all cases the amount of Cu may not be increased in the second reactor over that of the first.
- the minimum metal contamination of the catalyst before magnetic separation is preferably at least 500 ppm Ni + V; more preferably at least 1000 ppm Ni + V; and most preferably at least 1500 ppm Ni + V.
- the Conradson Carbon number in the first reactor is preferably in the range 0.1-2, more preferably in the range 0.1-1.5, and most preferably in the range 0.1-1 ; and the Conradson Carbon number in the second reactor corresponding to each of these ranges is preferably in the range 2-20; more preferably in the range 1.5-20; and most preferably 1-20.
- the magnetic cut can be done in three different cuts. For example, preferably at least 20% by weight of the more magnetically active material is discarded before transfer from the first cracker to the second; more preferably at least 50% by weight of the more magnetically active material is discarded; and most preferably at least 70% by weight of the more magnetically active material is discarded.
- An improvement in both yields and selectivity are found. The benefit occurs when a different feed stock from that in a first FCC unit is contacted in a second FCC unit with the magnetically separated FCC equilibrium catalyst from the one or more first FCC units.
- Iron and magnesium magnetic hooks were found to be preferable to heavy rare earth family magnetic hooks in many instances.
- the rate of addition of iron was preferably in the range of up to two to three times, and possibly more, the level of nickel and vanadium in the feedstock.
- the rate of addition of manganese is preferably at any rate between 0.1 ppm and 100 ppm, so as to deposit on total equilibrium catalyst in amount from 100 to 50,000 ppm.
- Example of a suitable manganese containing compounds are monocyclopentadiene tricarbonyl.
- suitable iron containing magnetic hooks are: sublime able iron trichloride and iron carbonyls, organic co pounds like ferrocene, or iron porphyrins, and water soluble salts such as ferrous acetate, ferric formate and ferrous or ferric sulfate.
- FIG. 1 is a schematic drawing of two FCC units and a magnetic separator.
- first FCC unit 10 which may represent more than one unit
- magnetic separator 11 which also represents one or more units
- second FCC unit 20 a series of conduits into and out of first FCC unit 10: conduit 12 for a first feedstock, conduit 13 for cold spent catalyst from other FCC units that are like the first FCC, conduit 14 for both magnetically separated cracking catalyst and fresh or make-up cracking catalyst, conduit 15 for a first portion of magnetically separated and recycled cracking catalyst, conduit 16 for product, conduit 17 for a second portion of magnetically separated cracking catalyst separated in first magnetic separator 11, conduit 18 for the contaminated catalyst from the first FCC unit, conduit 19 for a greater magnetic discard stream from the magnetic separator, and a series of conduits into and out of second FCC unit 20: conduit 22 for second feedstock, conduit 24 for make-up cracking catalyst, conduit 26 for product, conduit 27 for discarded catalyst.
- first FCC unit 10 a hydrocarbyl feedstock having the following characteristics is introduced through conduit 12 at a rate sufficient to give a flowing catalyst-to-oil weight ratio of 2.5 to 15.
- the riser cracker conditions of FCC unit 10 are: 0.1 to 3 seconds residence time, 350 to 550 input feed temperature, 890 to 1010°F outlet temperature, 0.01 to .5 lbs/barrel make-up catalyst rate.
- the riser cracker conditions of FCC unit 20 are: the same ranges as FCC #1.
- Catalyst recycle rate varies from 1 to 99% by wt., and percent rejection rate varies from 1 to 99% by wt. from magnetic separator 1 1.
- Rate of transfer of catalyst from first FCC unit 10 to magnetic separator 1 1 through conduit 18 in pounds (kilograms) per hour is 0 to 2 tons/hr. Rate of transfer through conduit 13 is from 0 to 2 tons/hr. Hydrocarbyl product exits through conduits 16 and 26, respectively.
- the respective properties of each product and feed entering and leaving from first and second FCC units, 10 and 20, respectively are given in the Example.
- Minimum metal content of ⁇ 1 ppm ⁇ 5 ppm each All or a portion of the feed to feed each of Ni, of Ni, V, Fe: the 2nd cracker generally has V, Fe, Cu Cu may be ⁇ 1 lower acquisition & fractioning ppm still (preparation) costs than the feed to the 1st cracker.
- 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.
- An example of a modification of this invention is the use of a second magnetic separator which separates equilibrium catalyst from the second cracker into fractions for recycle back into the second cracker or other processing unit.
- the cuts for rejecting catalyst in the magnetic separator from the second cracker are preferably at least 50%, more preferably at least 75% and most preferably at least 90%
- the amount of heavy rare earth family metals that are present on the catalyst in the second cracker are preferably in the range 5 to 10,000 ppm, more preferably in the range 100 to 5,000 ppm, and most preferably in the range 200-4000 ppm.
- any reference to a numerical range is intended to expressly incorporate herein by reference each and every numerical value within such range and each and every numerical range within such range.
- a given range of 1 to 100 is intended to include 23, a value within the given range of 1 to 100, and 10 to 70, a range within the given range.
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1996/001623 WO1997028233A1 (en) | 1994-05-10 | 1996-02-05 | Magnetically separated equilibrium catalyst for specialized cracking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0880571A1 true EP0880571A1 (de) | 1998-12-02 |
Family
ID=22254690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96903789A Withdrawn EP0880571A1 (de) | 1996-02-05 | 1996-02-05 | Magnetisch getrennte gleichgewichtkatalysator für spezialisiertes kracken |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0880571A1 (de) |
| AU (1) | AU4776496A (de) |
-
1996
- 1996-02-05 EP EP96903789A patent/EP0880571A1/de not_active Withdrawn
- 1996-02-05 AU AU47764/96A patent/AU4776496A/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9728233A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU4776496A (en) | 1997-08-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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| 17P | Request for examination filed |
Effective date: 19980804 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT NL SE |
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| 17Q | First examination report despatched |
Effective date: 19990730 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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| 18D | Application deemed to be withdrawn |
Effective date: 19991112 |