A process for converting residual oil comprising vacuum bottoms in the presence of a cracking catalyst of high surface area and comprising an ultrastable zeolite is described. More particularly, a conversion process particularly contributing to producing cycle oil and gasoline boiling range products with reduced carbon deposition in combination with a relatively high regeneration temperature operation of at least 1350° F. and above, and a short contact time riser hydrocarbon conversion operation contributing to reducing slurry oil product in favor of lower boiling products is described. A fluid cracking catalyst comprising a special ultrastable crystalline zeolite of high silica to alumina ratio provides hydrothermal stability of acceptable tolerance in the environment employed.
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14. A method for catalytically converting residual oils comprising vacuum bottoms which comprises,
converting said residual oil with a catalyst consisting of about 30-50 wt. % of ultrastable faujasite crystalline zeolite dispersed in a matrix material of clay and silica binder providing active cracking sites, said catalytic conversion effected at said residual oil pseudo-critical temperature for a time in the range of 0.5 to 3 seconds in a riser reaction zone, and recovering a product selectively of said catalytic conversion particularly comprising gasoline and light cycle oils comprising largely two member rings separately from catalyst particles comprising hydrocarbonaceous deposits of said conversion.
1. A method for upgrading increasing conversion to liquid products of a residual oil portion of crude oil boiling above 600° F. comprising metallo-organic compounds which comprises contacting a feed containing said residual portion of crude oil boiling above 600° F. said feed having a conradson carbon content above about 2.5 weight percent with a catalyst consisting of from 20 to 80 wt. % of an ultrastable faujasite crystalline zeolite dispersed in a silica-clay matrix for a time at a temperature particularly selective for conversion of the residual portion of crude oil to products of gasoline, light cycle oil and gasoline forming gaseous components, and
recovering said products comprising gasoline and light cycle oil selected from the group consisting of: silica-clay, silica-alumina, clay, silica, alumina and mixtures thereof, at a temperature above about 950° F. to provide a ratio of volume percent of light cycle oil to heavy cycle oil of in excess of 1.03 at essentially constant conversion and recover said light cycle oil and heavy cycle oil .
2. The method of
3. The method of
4. The method of
5. The method of
6. The method of
7. The method of
8. The method of claim 7 6 wherein the catalyst elevated said high temperature of said catalyst particles is achieved by burning hydrocarbonaceous deposits of said residual oil conversion and increases in response to the feed conradson carbon content at catalyst regeneration temperatures in the range of 1350° to 1600° F.
9. The method of
10. The method of
11. The method of
12. The method of
13. The method of
15. The method of
16. The method of
17. The method of
21. The method of claim 1 wherein said matrix has active cracking sites. 22. A method for increasing conversion to liquid products of a residual oil portion of crude oil feed boiling above 600° F. said method comprising: (a) contacting said feed having a conradson carbon content above about 2.5 weight percent with a catalyst consisting of from 20 to 80 wt. % of an ultrastable Y zeolite dispersed in a matrix said contacting (i) providing an increase in production of light cycle oil relative to heavy cycle oil to provide a ratio of volume percent of said light cycle oil to said heavy cycle oil in excess of 1.03 at essentially constant conversion and (ii) producing carbonaceous deposits on said catalyst; and (b) regenerating said catalyst by combusting said carbonaceous deposits in the substantial absence of hydrothermal deactivation of said catalyst wherein at least a portion of said regeneration occurs at a temperature of at least about 1350° F. 23. The method of claim 22 wherein said matrix is selected from the group consisting of silica-clay, silica-alumina, clay, silica, alumina, and mixtures thereof. 24. The method of claim 22 wherein said residual oil portion comprises components boiling above 1050° F. 25. The method of claim 24 wherein at least a portion of said regenerating is accomplished at a regenerator temperature of between about 1350° F. and about 1600° F. 26. The method of claim 11 wherein said ultrastable Y zeolite has a silica/alumina ratio of at least 3 and a unit cell size less than 24.65 Angstroms. 27. The method of claim 22 wherein a diluent material is used with the residual oil portion said diluent material comprising a material selected from the group consisting of steam, CO2, light normally gaseous hydrocarbons comprising C3 minus materials, and mixtures thereof in cooperation with spray nozzles. 28. The method of claim 22 wherein said regenerating removes said carbonaceous deposits on said catalyst to below about 0.25 weight percent. 29. The method of claim 23 wherein said matrix has active cracking sites. 30. The method of claim 22 wherein said contacting of the residual oil and catalyst is effected at a temperature in the range of about 950° F. to about 1400° F. 31. The method of claim 22, wherein said contacting of the residual oil and catalyst is effected at a temperature equal to or above the crude oil pseudo-critical temperature. 32. In a method for upgrading an oil feed containing residual oil boiling above 600° F. wherein said residual oil is contacted with a cracking catalyst the improvement comprising: providing an increase in production of light cycle oil compared to heavy cycle oil and yield a ratio volume percent of light cycle oil to heavy cycle oil in excess of about 1.03 at essentially constant conversion and an increase in conversion to C3 and heavier liquid products by contacting said residual oil with a catalyst which maintains an equilibrium surface area in excess of 65 m2 /gm wherein said catalyst comprises 20 to 80 wt. % ultrastable Y zeolite on a matrix and recovering said light cycle oil and heavy cycle oil. 33. The method of claim 32 wherein carbonaceous deposits are formed on said catalyst by contacting said residual oil and said catalyst containing said deposits is regenerated by combusting said carbonaceous deposits at a temperature of at least about 1350° F. and wherein said equilibrium surface area is at least about 105 m2 /gm. 34. The method of claim 32 wherein said catalyst is contacted with said residual oil at a temperature of at least about 950° F. 35. The method of claim 32 wherein said matrix is selected from the group consisting of silica-clay, silica-alumina, clay, silica, alumina and mixtures thereof. 36. The method of claim 35 wherein said matrix has active cracking sites. 37. The method of claim 35 wherein carbonaceous deposits found on said catalyst when said catalyst contacts said residual oil are combusted at a temperature of at least about 1350° F. to provide a regenerated catalyst. 38. The method of claim 35 wherein said catalyst is contacted with said residual oil at a temperature equal to or above the pseudo-critical temperature of said crude oil. 39. The method of claim 32 wherein said contacting is effected at a temperature between about 950° F. and 1400° F. and produces carbonaceous deposits on said catalyst, said catalyst containing said deposits being regenerated by combusting said deposits to provide a regeneration temperature in the range of about 1350° F. to 1600° F. 40. The method of claim 39 wherein said regeneration temperature is at least about 1400° F. 41. The method of claim 22 wherein at least a portion of said regeneration occurs at a temperature of at least about 1400° F. |
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The drawing is a graphical representation of the contraction of an ultrastable crystalline zeolite obtained during calcination under different temperature conditions. It is observed that this contraction is substantially less than that obtained when subjecting a CREY catalyst composition to similar conditions.
A class of zeolite containing catalysts particularly suitable for use in the residual oil conversion process of this invention is one comprising an ultra stable crystalline zeolite commercially identified as Z-14US. The preparation of an ultrastable crystalline zeolite discussed above is described in U.S. Pat. No. 4,287,048, and referenced material including U.S. Pat. Nos. 3,293,192 (1966) and 3,402,966, the subject matter of which is incorporated herein by reference.
The ultrastable sieve or crystalline zeolite described in the above identified referenced material and U.S. patents are characterized by a significant (1-1.5%) decrease in the unit cell dimensions of the parent sodium zeolite. This contraction is caused by extraction of aluminum cations from the crystalline zeolite in the manufacturing process. This has been shown to be true by McDaniel and Maher in their book entitled "Zeolite Chemistry and Catalysis", page 320 by FIG. 17 and reproduced for inclusion herewith as the drawing. In this drawing the shaded area identifies the unit cell contraction area for ultrastable zeolites of different silica to alumina ratio.
To be a suitable ultrastable crystalline zeolite component of the catalyst for use in the process of this invention, the zeolite SiO2 /Al2 O3 ratio is greater than 3 and the unit cell size or lattice constant is less than 24.65 Angstroms. In particular embodiment, the ultrastable zeolite will have a SiO2/Al2 O3 ratio of at least 5 with a unit cell size of about 24.5 Angstroms or less. A high sodium content zeolite, matrix components and residual oil feed are known to deactivate a cracking catalysts zeolite crystalline structure relativity rapidly so it is important to reduce the sodium content of these materials and particularly the finished zeolite sodium content to at least 1 weight percent or less. Various techniques for achieving this low sodium content are discussed in the literature. Preferably the residual Na2 O on the zeolite structure is below 0.5 weight percent.
The cracking activity level of an ultrastable crystalline zeolite is less than a rare earth exchanged zeolite such as CREY. Thus it requires considerably more ultrastable zeolite than CREY to form catalyst particles of the same degree of activity. This high addition has been considered heretofore as not suitable for use in hydrocarbon conversion operations of lower regenerator temperatures.
Modern high activity FCC catalysts are reported to contain in the range of 15-40% of a rare earth type Y zeolite. In a conventional rare-earth zeolite catalyst employed in an FCC unit processing gas oils and operating with regenerator temperatures generally maintained below 1400° F. and more usually not above 1350° F. or less requires using for the same activity level an ultrastable crystalline zeolite catalyst comprising from 60-160% of the ultrastable zeolite. Obviously, no catalyst could contain more than 100% of any component. A catalyst particle of such high zeolite content presents formidable problems to the catalyst suppliers and manufacturer to produce such a catalyst composition with suitable physical attrition resistant or hardness properties for use in a circulating fluid catalytic cracking system.
At relatively high regenerator temperatures in the range of 1350° F.-1600° F. and required in the high temperature conversion of residual oils an ultrastable crystalline zeolite catalyst obtained as above provided is found to give an equilibrium activity that is equal to or exceeds that of a rare-earth type Y sieve (CREY) containing catalyst and provides a higher equilibrium surface area without encountering undesired coke and liquid product selectivity as herein identified. It has also been found that at a high oil feed--catalyst suspension mix temperatures at least equal to the pseudo critical temperature of the feed and characterized by regenerated catalyst temperatures at or above 1350° F. the heavy or high boiling multi ring components in the oil feed are more readily converted thermally and catalytically to lower boiling desired products by the high surface area ultrastable zeolite catalyst in modern catalytic cracking facilities.
A commercial test of the ultrastable hydrogen form of crystalline zeolite containing catalyst herein identified provides the data shown in Table I. In this operation where the regenerator was operating over 1400° F., the ultrastable zeolite containing catalyst actually out-performed a CREY catalyst. That is, lower coke yields were observed and there is a substantial drop in the heavy cycle oil yield and its gravity. Extra light cycle oil and gasoline is produced at the expense of coke and heavy cycle oil with liquid C3 plus yield increased significantly and all factors resulting in economic gain.
| TABLE I |
| ______________________________________ |
| COMMERCIAL CRACKING PERFORMANCE |
| Type Zeolite in Catalyst* |
| Z-14US** C--RE--Y |
| ______________________________________ |
| CAT ADDN's #/Bbl. FEED |
| .34 .4 |
| FEED RATE, B/D 18.070 18.000 |
| FEED CON. CARBON, Wt. % |
| 2.5 2.5 |
| Rx. TEMP. °F. |
| 982 974 |
| REGEN. DENSE PHASE TEMP. |
| 1.413 1.402 |
| °F. |
| CONVERSION, VOL. % 80.8 80.1 |
| C2 - YIELD, SCFB |
| 312 324 |
| ALKYL FEED, VOL. 5 (C3 -C4) |
| 26.7 26.1 |
| GASOLINE, VOL. % 58.1 55.7 |
| LCO, VOL. % 12.8 10.1 |
| SLURRY, VOL. % 6.4 9.8 |
| TOTAL LIQUID YIELD 104.0 101.7 |
| C3 + VOL. % |
| COKE, Wt. % 5.6 6.4 |
| MICRO ACTIVITY 60 70 |
| CATALYST SURFACE AREA |
| 105 65 |
| M2 /gm |
| ______________________________________ |
| *Catalysts contained approximately same amount of zeolite promoter (Wt. |
| basis) when new. |
| **Z14US refers to ultrastable zeolites. |
The reduction in heavy cycle oil product and increased light cycle oil product obtained as above-identified was surprisingly unexpected when compared to the results obtained with a rare-earth exchanged crystalline zeolite (CREY) containing catalyst. Both forms of zeolite catalysts were supported by a relatively inactive matrix material. The increase in equilibrium surface area indicates that substantially more zeolite is present in the equilibrium catalyst comprising the ultrastable hydrogen form zeolite containing catalyst.
| TABLE II |
| ______________________________________ |
| Catalyst Sieve Type |
| US RE--Y |
| Matrix Type Low surface Area/Activity |
| Equil. S.A. 105 65 |
| ______________________________________ |
The large surface area of the ultrastable zeolite is apparently very effective in providing active accessible cracking sites to cause the experienced molecular weight reduction in the slurry oil. Unlike cracking with amorphous cracking catalysts, it is observed that the ultrastable hydrogen zeolites do this cracking with less or a lower coke and gas production. The data provided in Table I clearly indicates that the equilibrium activities of the two catalysts, ultrastable zeolite and rare earth exchanged zeolite, after exposure to regenerator temperatures of about 1400° F., were quite similar in activity even though the CREY catalyst started with 3-4 times the activity of the ultrastable zeolite catalyst. At even higher regenerator temperatures, the benefits obtained by using the ultrastable catalyst are expected to be even greater.
The following conclusions are reached in view of the above with respect to the fluid catalytic cracking of residual oil with an ultrastable crystalline zeolite catalyst.
1. High catalyst temperatures at point of oil catalyst contact, vis-a-vis, high regenerator temperatures are necessary to more completely vaporize the high boiling residual oil feed stock.
2. Failure to adequately vaporize-atomize the feed encourages poor cracking selectivity i.e., encourages high coke make, high cycle oil production, particularly cycle oils rich in ring structures greater than 2 member rings, high gas make and low gasoline production. The poor performance attributed when the feed is inadequately vaporized is likely due to the "coke shut off" of the active catalyst sites by the portion of the feed not vaporized.
3. As the residual oil content of the feed stock increases the catalyst high temperature at point of oil contact (vis-a-vis high regenerator temperature) must be permitted to rise to a higher optimum level in order to encourage more nearly complete vaporization of the feed if undesirable cracking selectivity is to be avoided.
4. Utilization of catalysts containing rare earth exchanged zeolites is inconsistent with high temperature regeneration despite their inherent relatively high initial activity, because of rapid surface area decay and rapid loss of activity in high temperature regeneration environment.
5. Ultrastable sieve or crystalline zeolite containing catalysts despite their relatively low fresh catalyst activity equilibrate in a commercial cracking process when cracking residual oil at desired high temperature conditions at acceptable catalyst activity levels and retain a desired high surface area. This high surface area equilibrium leads to desirable cracking selectivity i.e., high yields of gasoline and gasoline forming components, increased yields of cycle oils containing two member rings produced at the expense of cycle oils containing higher member rings with substantially less coke make and a reduced gas production.
The ultrastable zeolite may be supported by any one of a different member of support materials or matrices. For example, matrices other than an inactive kaolin-clay silicon oxide binder combination can be used to hold or include the ultrastable hydrogen exchanged crystalline zeolite. In fact, any of the known prior art or conventional catalyst matrix materials can be used. Such materials would include synthetic silica-alumina, clay, silica or alumina binders or any combination thereof. The finished catalyst will preferably contain not less than 20 wt % or more than 80% of an ultrastable hydrogen form of crystalline zeolite herein identified.
The ultrastable crystalline "Y" zeolite catalyst preferably employed by this invention for cracking high boiling residual oils may be used however, in conjunction with a metal entrapment material or metals sink for accumulation thereof. The finished catalyst will preferably contain not less than 20 wt % or more than 80% of an ultrastable hydrogen form of crystalline zeolite herein identified.
The catalytic cracking or conversion of high boiling hydrocarbons comprising Conradson carbon producing materials are best catalytically converted in a highly vaporized-atomized condition during contact with the high surface area zeolite containing catalyst herein particularly defined by employing contact temperature conditions provided by hot regenerated catalyst at least equal to the feed pseudo-critical temperature. Thus the catalyst regeneration temperature will increase above 1350° F. during combustion of deposited carbonaceous material as the residual oil feed Conradson carbon value increases even though the ultrastable zeolite catalyst composition employed in the conversion process of this invention contributes to a reduction in coke make. Thus when processing vacuum gas oils comprising the resid portion of the crude oil, regeneration temperatures above 1350° F. and up to as high as 1600° F. or more can be experienced as carbonaceous deposits increase in response to the feed Conradson carbon content.
The catalytic conversion operation of this invention is preferably one of relatively short vaporized hydrocarbon contact with the special catalyst composition comprising from 20 to 80 wt % of ultrastable crystalline zeolite as a dispersed catalyst phase in a riser contact zone wherein the hydrocarbon residence time in contact with catalyst particles can be restricted to within the range of 0.5 to 5 seconds and more usually in the range of 1 to 3 seconds. This dispersed catalyst phase-vaporized hydrocarbon contact may be implemented in substantial measure by the use of an atomizing diluent material with the high boiling hydrocarbon feed. Diluent materials suitable for this purpose include steam, CO2, light normally gaseous hydrocarbons comprising C3 minus material or a combination thereof in an amount which will reduce the high boiling feed partial pressure and achieve desired atomized-vaporized dispersion contact of hydrocarbon feed with high temperature catalyst particles. Atomization of the feed may be substantially implemented by use of appropriate spray nozzles. Thus the operating parameters to achieve an optomized contact between feed and catalyst particles also include feed exit velocities in excess of 10 feet per second to achieve atomized spraying of the feed with or without diluent material across a riser reactor cross section for intimate contact with hot catalyst particles charged thereto.
The above identified operating parameters are intended to also accelerate the mixture relatively uniformly within the feed vaporization section of a riser reactor in a minimum time frame and thus enhance rapid heat transfer from hot catalyst particles to charged feed preferably atomized and thus prevent localized enhanced catalyst to oil ratios contributing to a dense catalyst bed phase. That is, the operating conditions and methods for implementing are selected to ensure a relatively dilute phase suspension contact between catalyst particles and atomized oil feed for vaporized conversion transfer through a riser conversion zone. Such dilute catalyst phase operations include catalyst particle concentrations in the range of 2 to 10 pounds per cubic foot and preferably not above about 5 pounds per cubic foot.
The catalyst hydrocarbon feed suspension formed as above provided is passed through a riser contact zone for a hydrocarbon contact time less than about 5 seconds before discharge therefrom at a temperature sufficiently elevated to maximize recovery of vaporized hydrocarbon material separately from catalyst particles.
In a more particular and specific aspect the present invention is directed to the catalytic conversion of high boiling residual oils comprising vacuum gas oils containing high boiling Conradson carbon producing materials employing a special ultrastable crystalline zeolite containing catalyst at a temperature equal to or above the feed pseudo-critical temperature in preferably a riser contact zone for a hydrocarbon residence time in the range of 0.5 to about 5 seconds and more usually not above about 3 seconds.
Thus as the end boiling point of the hydrocarbon feed or the Conradson carbon level thereof increases so also will the catalyst regeneration temperature generally increased in response to increased deposited carbonaceous material removed by combustion and contributing to high temperature regeneration and conversion of the feed according to the concepts of this invention. However, as discussed above, employing the ultrastable zeolite catalyst provides a lower coke yield than obtained with the rare earth zeolite catalyst thus contributing measurably to the advantages of the processing concepts of this invention as herein described.
Depending on the feed hydrocarbon to be converted, its boiling range and Conradson carbon contributing factor, the hydrocarbon conversion operation may be effected at a temperature in the range of 950° F. up to about 1400° F. or at a temperature equal to or above the feed pseudo-critical temperature employing a reactor pressure from about atmospheric pressure up to about 100 psig but generally not above about 50 psig.
The riser cracking operation of this invention may be employed in conjunction with the catalyst regeneration arrangement of copending application Ser. No. 169,086, filed July 15, 1980 (now U.S. Pat. No. 4,332,674), the subject matter of which is incorporated herein by reference thereto. That is, the apparatus and operating concepts of the above identified application and the methods of implementation except as particularly modified by employing an ultrastable crystalline zeolite containing catalyst, as herein provided, may be employed with considerable advantage in protecting the activity and selectivity characteristics of the ultrastable crystalline zeolite catalyst particularly when reducing residual coke on the ultrastable zeolite catalyst to less than about 0.25 wt. %.
Having thus generally described the method and concepts of this invention and discussion specific embodiments in support thereof, it is to be understood that no undue restrictions are to be imposed by reasons thereof except as defined by the following claims.
Letzsch, Warren S., Dean, Robert R., Mauleon, Jean L.
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