EP0074501A2
Expired / Lapsed
EP
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Process and catalyst for the conversion of oils that contain carbon precursors and heavy metals
Assignee: Ashland LLC
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Filing: 1982-08-16
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Granted: —
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Expires: 2002-08-16
Abstract
Abstract An improved process and catalyst for economically converting carbo-metallic oils to lighter products. This process is practiced in accordance with effective metals management, carbon management and catalyst activity management combined with feed atomization-vaporization, efficient stripping of carbonaceous material from the coked catalyst, exothermic and endothermic removal of hydrocarbonaceous material to effectively maintain the RCC unit in heat balance. This reduced crude cracking process is practiced with a new and improved catalyst composition identified as RCCC-1 Special that is characterized by the following composition; at least 30 wt% rare earth exchanged "Y" faujasite crystalline zeolite with a silica to alumina ratio of at least 5 of a high lanthanum to cerium ratio and residual sodium content less than 0.30 wt%, is provided with a pore volume greater that 0.35 cc/gm and comprises a clay matrix material that may or may not be acidic with pore size openings in the range of 500 to 2,000 angstroms. The RCCC-1 Special can contain metal promoters to catalyze the endothermic removal of coke and the partial removal of hydrogen present in the carbonaceous material with carbon dioxide. In addition, metal additives to passivate and immobilize vanadium is comtemplated.
Inventors
- 👤 Oliver J. Zandona
- 👤 William P. Hettinger, Jr.
- 👤 Stephen M. Kovach
- 👤 Wayne H. Beck
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-04 04:30
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/08; B01J29/084; C; C10; C10G; C10G11/00; C10G11/02; C10G11/04; C10G11/05; C10G11/14; C10G11/18; Y; Y02; Y02P; Y02P30/00; Y02P30/40
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
170 words
In the process for catalytically cracking a reduced crude feed comprising metal contaminants and Conradson carbon producing components, the improvement which comprises effecting the catalytic cracking of a reduced crude boiling above 650°F at a temperature within the range of 950 and 1100°F in the presence of a diluent material such as dry gas, naphthas, steam and water sufficient to substantially reduce the partial pressure of the oil feed below atmospheric pressure, and employing as a special catalyst in said reduced crude cracking operation a composition of matter comprising, at least about 30 wt% of calcined rare earth exchange "Y" crystalline zeolite of high lanthanum to cerium ratio, said catalyst providing a pore volume greater than 0.35 cc/gm comprising a matrix material providing a substantial percentage of pore size in the range of 500 to 2000 angstroms, said catalyst composition comprising less than 0.30% sodium, a zeolite silica to alumina ratio of at least 5 and said catalyst prepared under conditions to provide an acidic matrix comprising said crystalline zeolite.
Claim 2
Dependent Claim
170 words
In the process for catalytically cracking a reduced crude feed comprising metal contaminants and Conradson carbon producing components, the improvement which comprises effecting the catalytic cracking of a reduced crude boiling above 650°F at a temperature within the range of 950 and 1100°F in the presence of a diluent material such as dry gas, naphthas, steam and water sufficient to substantially reduce the partial pressure of the oil feed below atmospheric pressure, and employing as a special catalyst in said reduced crude cracking operation a composition of matter comprising, at least about 30 wt% of calcined rare earth exchange "Y" crystalline zeolite of high lanthanum to cerium ratio, said catalyst providing a pore volume greater than 0.35 cc/gm comprising a matrix material providing a substantial percentage of pore size in the range of 500 to 2000 angstroms, said catalyst composition comprising less than 0.30% sodium, a zeolite silica to alumina ratio of at least 5 and said catalyst prepared under conditions to provide an acidic matrix comprising said crystalline zeolite.
Claim 3
Dependent Claim
70 words
The process of Claim 1 wherein the reduced crude comprises material boiling above 1025°F and the catalyst charged to the reduced crude cracking operation comprises less than 0.1 wt% carbon. The process of Claim 1 wherein the catalyst comprises at least about 35 wt% of the zeolite and wherein the catalyst circulated between the cracking zone and a catalyst regeneration zone comprises at least about 5000 ppm Ni + V.
Claim 4
Dependent Claim
38 words
The process of Claim 1 wherein the vaporous hydrocarbon residence time in contact with the catalyst is restricted to less than 3 seconds and wherein the catalyst is regenerated under conditions to restrict the catalyst temperatures below 1500°F.
Claim 5
Dependent Claim
69 words
The process of Claim 1 wherein hydrogen is charged with the feed and catalyst particles comprising hydrocarbonaceous deposits are stripped with C0 2 to react with hydrogen and form CO plus water recovered with hydrocarbon conversion products and wherein the stripped catalyst is passed through a sequence of catalyst regeneration zones temperature restricted not to exceed about 1400°F and provide a catalyst of low residual carbon below 0.1 wt%.
Claim 6
Independent Claim
209 words
A method for catalytically cracking reduced crudes comprising significant Conradson carbon values and a high vanadium to nickel ratio of metal contaminants which comprises, contacting said reduced crude feed in the presence of gasiform diluent material with a cracking catalyst of at least 35 wt% of a calcined rare earth exchanged crystalline "Y" faujasite zeolite dispersed in a clay matrix material providing a substantial portion of its pore openings within the range of 500 to 2000 angstroms, said zeolite comprising a high LA/Ce ratio greater than 1/1 and said catalyst composition having a pore volume of at least 0.35 cc/ g m, said contact between said reduced crude and said catalyst effected at a temperature of at least 1000°F for a vaporous hydrocarbon residence time within the range of 1 to 2 seconds whereby deposition of hydrocarbonaceous material on the catalyst is at least equal to 12 wt% based on feed, said catalyst used in an operating time period to provide an equilibrium catalyst comprising Ni + V metals accumulation in the range of about 5000 to about 25,000 ppm, maintaining a conversion level during said cracking operation comprising dry gas, C 5 minus gasiform hydrocarbons, a C 5 + gasoline fraction and light and heavy fuel oil products.
Claim 7
Independent Claim
209 words
A method for catalytically cracking reduced crudes comprising significant Conradson carbon values and a high vanadium to nickel ratio of metal contaminants which comprises, contacting said reduced crude feed in the presence of gasiform diluent material with a cracking catalyst of at least 35 wt% of a calcined rare earth exchanged crystalline "Y" faujasite zeolite dispersed in a clay matrix material providing a substantial portion of its pore openings within the range of 500 to 2000 angstroms, said zeolite comprising a high LA/Ce ratio greater than 1/1 and said catalyst composition having a pore volume of at least 0.35 cc/ g m, said contact between said reduced crude and said catalyst effected at a temperature of at least 1000°F for a vaporous hydrocarbon residence time within the range of 1 to 2 seconds whereby deposition of hydrocarbonaceous material on the catalyst is at least equal to 12 wt% based on feed, said catalyst used in an operating time period to provide an equilibrium catalyst comprising Ni + V metals accumulation in the range of about 5000 to about 25,000 ppm, maintaining a conversion level during said cracking operation comprising dry gas, C 5 minus gasiform hydrocarbons, a C 5 + gasoline fraction and light and heavy fuel oil products.
Claim 8
Dependent Claim
249 words
The method of Claim 5 wherein the catalyst comprising hydrocarbonaceous material deposits is stripped under a relatively high temperature stripping condition and thereafter hydrocarbonaceous deposits are removed from the catalyst in a catalyst regeneration operation comprising oxygen regeneration alone or in combination with endothermic removal of carbonaceous material with C0 2 to provide a regenerated catalyst at a temperature within the range of 1350 to 1500°F comprising less than 0.1 wt% residual carbon on the catalyst or wherein regeneration of the catalyst is accomplished in at least two separate stages of catalyst contact with oxygen containing gas under temperature conditions restricted to within the range of 1250 to 1500°F to provide a regenerated catalyst comprising less than 0.05 wt% of residual carbon in the catalyst or wherein regeneration of the catalyst is accomplished in separate stages of regeneration wherein C0 2 is relied upon to react with carbon in carbonaceous deposits under endothermic reaction conditions in one of the stages of regeneration and an oxygen containing gas is relied upon in another stage of regeneration to remove carbonaceous material by burning to produce a CO rich flue gas recovered therefrom and said stages of catalyst regeneration are effected under temperature conditions restricted to below 1500°F and wherein the catalyst composition comprises at least about 35 wt% of said crystalline zeolite less than 0.30 wt% Na 2 O and deposited vanadium is immobilized by forming a high melting temperature composition above 1500°F with an additive material suitable for the purpose.
Claim 9
Dependent Claim
27 words
The process of Claim 5 wherein stripping of hydrocarbonaceous material is accomplished with C0 2 to form CO and water by reaction with hydrogen associated with carbon.
Claim 10
Dependent Claim
35 words
The process of Claim 5 wherein the diluent material is employed with the reduced crude feed comprises one or more of steam water, naphtha, C 5 minus hydrocarbons, a hydrogen donor material, and dry gas.
Claim 11
Dependent Claim
101 words
A catalyst composition for cracking hydrocarbons boiling above 650°F and comprising carbo-metallic impurities of naphthenes and asphaltenes comprising at least about 35 wt% of a calcined rare earth exchanged "Y" crystalline faujasite dispersed in a clay containing matrix material, said catalyst composition providing a pore volume of at least 0.35 cc/g, a matrix providing a substantial amount of pore size openings within the range of 500 to 2000 A, said catalyst composition comprising a residual sodium content of less the 0.30 wt% and said catalyst composition rare earth exchanged during preparation to provide a lanthanum to cerium ratio greater that 1/1.
Claim 12
Dependent Claim
101 words
A catalyst composition for cracking hydrocarbons boiling above 650°F and comprising carbo-metallic impurities of naphthenes and asphaltenes comprising at least about 35 wt% of a calcined rare earth exchanged "Y" crystalline faujasite dispersed in a clay containing matrix material, said catalyst composition providing a pore volume of at least 0.35 cc/g, a matrix providing a substantial amount of pore size openings within the range of 500 to 2000 A, said catalyst composition comprising a residual sodium content of less the 0.30 wt% and said catalyst composition rare earth exchanged during preparation to provide a lanthanum to cerium ratio greater that 1/1.
Claim 13
Dependent Claim
69 words
A catalyst composition comprising greater that 30 wt% of rare earth exchanged "Y" faujasite zeolite of a lanthanum to cerium ratio greater that 1/1, said zeolite dispersed in a kaolin matrix material providing pore size openings in the range of 500 to 2000 angstroms and said catalyst composition comprising less than 0.30 wt% residual sodium after multiple exchanges with a high ratio of lanthanum to cerium rare earth mixture.
Claim 14
Dependent Claim
69 words
A catalyst composition comprising greater that 30 wt% of rare earth exchanged "Y" faujasite zeolite of a lanthanum to cerium ratio greater that 1/1, said zeolite dispersed in a kaolin matrix material providing pore size openings in the range of 500 to 2000 angstroms and said catalyst composition comprising less than 0.30 wt% residual sodium after multiple exchanges with a high ratio of lanthanum to cerium rare earth mixture.
References Cited (Backward Citations)
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