US3891538A - Integrated hydrocarbon conversion process - Google Patents
Integrated hydrocarbon conversion process Download PDFInfo
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- US3891538A US3891538A US372117A US37211773A US3891538A US 3891538 A US3891538 A US 3891538A US 372117 A US372117 A US 372117A US 37211773 A US37211773 A US 37211773A US 3891538 A US3891538 A US 3891538A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
Definitions
- United States Patent 1 1 Walkey INTEGRATED HYDROCARBON CONVERSION PROCESS [75] Inventor: John E. Walkey, Richmond, Calif. [73] Assignee: Chevron Research Company, San Francisco, Calif.
- the subject invention is directed to the combination of three processes in a unique manner which concurrently improves (1) product yields and product qualities from the combined processes while (2) improving the efficiency of all three processes.
- An integrated hydrocarbon conversion process for converting a heavy hydrocarbon feedstock boiling above 650F. into various valuable products including gasoline, jet fuel, and coke which comprises:
- hydrodesulfurizing the feedstock in a hydrodesulfurization zone thereby obtaining an effluent comprising gasoline, jet fuel, a fraction comprising material boiling in the range of from about 650 to about 1000F., and a fraction comprising material boiling above about l000F.;
- the subject invention is directed to an integrated hydrocarbon conversion process for converting heavy hydrocarbon feedstocks boiling above 650F. and containing substantial quantities of materials boiling above l000F. into various valuable products in good yield and with good selectivity for producing the more valuable products.
- the process of the subject invention utilizes a hydrodesulfurization zone, a catalytic cracking zone, and a coker, in a particular mode of operation which optimizes the operating efficiency of all three units.
- diesel fuel may be recovered as well as middle distillates for use as fuel oil.
- Light gases are also produced which may be handled by conventional means and used for conventional purposes.
- the heavy hydrocarbon feedstocks utilized in the subject invention comprise hydrocarbons boiling above about 650F. and contain substantial quantities of material boiling above I000"F.
- a typical feedstock is that normally produced as the residuum product from atmospheric-pressure distillation of crude oil.
- the initial boiling point of the feedstock can be as low as about 350F. if it is desired to hydrodesulfurize the 350 to 650F. boiling range fraction in the crude oil.
- Other feedstocks include heavy hydrocarbons recovered from tar sands, synthetic crude oil recovered from oil shales, heavy oils produced from liquefaction of coal, etc.
- the hydrocarbon feedstocks will generally contain at least about 10 percent of materials boiling above I000F.
- Hydrodesulfurization of the heavy hydrocarbon feedstock is carried out at conventional operating conditions which will generally include a temperature in the range of about 650 to about 850F., preferably within the range of from about 700 to about 800F., a liquid hourly space velocity of from about 0.1 to about 3, preferably about 0.3 to about L5, and a pressure of from about 500 to about 3,000 psig, preferably about 1,000 to about 2,000 psig.
- the hydrogen supply rate (makeup and recycle hydrogen) to the hydrodesulfurization zone will generally be in the range of from about 500 to 20,000 SCF/barrel, preferably in the range from about 1,000 to about 10,000 SCF/barrel of feed, and more preferably in the range of from about 2,000 to about 4,000 SCF/barrel.
- hydrodesulfurization of the hydrocarbon feedstock fed to the hydrodesulfurization zone is the primary purpose of this zone, other reactions encompassed within the term hydroconversion, e.g., hydrogenation and hydrodenitrification, may be occurring.
- the hydrodesulfurization catalyst utilized in the subject invention can comprise any conventional hydrodesulfurization catalyst. Normally these catalysts comprise composites comprising at least one hydrogenating component selected from Group VI metals and compounds of Group V] metals and at least one hydrogenating component selected from Group VIII metals and compounds of Group VIII metals together with a refractory support such as alumina, silica-alumina, silicaalumina-titania, and combinations of amorphous inorganic oxides with a zeolite.
- a refractory support such as alumina, silica-alumina, silicaalumina-titania, and combinations of amorphous inorganic oxides with a zeolite.
- a preferred hydrodesulfurization catalyst comprises a carrier of alumina in which discrete, substantially insoluble metal phosphate particles are dispersed in said carrier and consisting essentially of at least one metal phosphate selected from phosphates of the zirconium, titanium, tin, thorium, cerium and hafnium, and containing substantially the entire phosphorus content of the said catalyst.
- Preferred insoluble metal phosphate components are phosphates of zirconium and titanium.
- Operating conditions utilized in the catalytic cracking zone of the subject invention are those conventional in catalytic cracking of hydrocarbon feedstocks. These generally include a temperature in the range of from about 850 to about llF., a pressure in the range of from about 1 to about 100 psig, preferably to 30 psig. The liquid hourly space velocities within the catalytic cracking zone will generally fall within the range of from about 1.5 to about 50, although space velocities as high as I00 or more in riser cracking units may be used. Preferred temperatures for use in the catalytic cracking zone will generally fall within the range of from about 850 to about I050F.
- the catalytic cracking process step including regeneration of the catalyst may be performed utilizing wellknown techniques, including, for example, fluidized bed or moving bed processes.
- the catalysts used in the catalytic cracking zone in the process of the present invention are those conventionally utilized in catalytic cracking processes.
- activated, naturally occurring catalytic cracking catalysts such as clay, i.e., kaolin
- synthetic clays such as those disclosed in U.S. Pat. No. 3,252,889
- semi-synthetic catalysts such as silica-alumina to which kaolin has been added.
- Synthetically prepared cracking catalysts containing amorphous silica-alumina, with or without additional promoters can also be used.
- ZeoIite-containing catalysts may also be used to reduce coke formation.
- crystalline zeolitic aluminosilicate catalysts are disclosed and discussed in great detail in U.S. Pat. Nos. 3,2l0,267 and 3,27I,4l8.
- the crystalline zeolitic molecular sieve component may have included therewith an amorphous matrix, for example, silicaalumina, titania, zirconia, magnesia, and the like.
- the coking zone in the subject invention utilizes conventional operating techniques and conditions. Typically, it may comprise either one of two different types of coking steps; namely, delayed coking or fluid coking. These are described in detail in U.S. Pat. No. 3,493,489, the disclosure of which is hereby incorporated by reference. Additional patents including U.S. Pat Nos. 3,537,975 and 3,5l8,l82 discuss fluid coking and delayed coking, respectively.
- decant oil means the heavy bottoms fraction of the effluent from the catalytic cracking zone. Typically it will boil in the range 800 to about I000F.
- the catalytic cracking cycle oil which is recycled (at least in part) to the hydrodesulfurization may encompass both the light cycle oil typically boiling in the range 430 to 650F., and the heavy cycle oil typically boiling in the range 650 to 800F. Part of this catalytic cracker cycle oil may also be recovered for use as fuel oil.
- the coker gas oil typically boils in the range of 400 to 900F.
- Cf means hydrocarbons having 4 or less carbon atoms.
- Cf hydrocarbons recovered in fractionator 5 will be saturated.
- the C, hydrocarbon fraction will contain unsaturated hydrocarbons.
- the C hydrocarbon fraction from fractionator I5 may also contain unsaturated compounds.
- an atmospheric residuum boiling above 650F. is fed by line 1 to hydrodesulfurization zone 2.
- Hydrogen is introduced into hydrodesulfurization zone 2 via line 3.
- the effluent from hydrodesulfurization zone 2 is fed by line 4 to fractionator 5 where various cuts are taken off as noted in the drawing.
- This fractionator may consist of two stages, i.e., an atmospheric column and a vacuum column.
- a fraction comprising hydrocarbons boiling in the range of from 650 to l000F. is fed by line 6 to eatalytic cracking zone 7.
- the effluent from catalytic cracking zone 7 is fed by line 8 to fractionator 9 wherein various cuts are obtained, as indicated in the drawing.
- a catalytic cracking cycle oil which comprises material boiling in the range of 430 to 800F. is removed by line 10 and recycled to hydrodesulfurization zone 2.
- a decant oil comprising material boiling above about 800F. and primarily in the range of 800 to I000F. is removed by line I1 and sent by lines ll and 12 to coking zone 13. Additional feed to coking zone 13 comprises the material boiling above I000F. from hydrodesulfurization zone 2. This material is fed to coking zone I3 by line 12.
- the effluent from coking zone 13 is sent by line 14 to a fractionator 15 wherein various cuts are removed as noted in the drawing.
- a coker gas oil is recycled by line 16 to hydrodesulfurization zone 2. Coke is removed by line 17.
- liquid products including gasoline, jet fuel, diesel fuel as desired, and coke are obtained in good yield and with high selectivity for the most desirable products, e.g., gasoline and jet fuel.
- the feed to the catalytic cracking zone is desulfurized and hydrogenated in hydrodesulfurization zone 2.
- the catalytic cracking cycle oil is recycled to the hydrodcsulfurization zone to improve its quality as a product and as feedstock to the catalytic cracking zone.
- distillate stocks i.e., a catalytic cracking zone cycle oil and coker gas oil.
- a catalytic cracking zone cycle oil and coker gas oil into the hydrodesulfurization zone together with the hydrocarbon feedstock. From the standpoint of operating efficiency, this is more effective than utilizing separate hydrodesulfurization zones for these materials.
- improved desulfurization can be obtained by combining lower boiling components. i.e.. cycle oil from the catalytic cracking zone and coker gas oil with the heavy hydrocarbon feedstock to a desulfurization zone. Further. hydrodesulfurization of the coker feed improves the yields and the quality of products from the coking zone.
- the unique integrated combination of processing steps of the subject invention provide improved feedstocks to each of the three processing zones. Improved operating efficiency results together with improved yields of high quality products.
- the catalyst in said hydrotreating zone comprises a Group Vl-B component, a Group VIII component, a refractory component and insoluble metal phosphate particles dispersed through said refractory component.
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Abstract
An integrated hydrocarbon conversion process for converting a heavy hydrocarbon feedstock boiling above 650*F. into various valuable products including gasoline, jet fuel, and coke, which comprises: A. HYDRODESULFURIZING THE FEEDSTOCK IN A HYDRODESULFURIZATION ZONE; B. CATALYTICALLY CRACKING AT LEAST A PORTION OF THE FRACTION FROM THE HYDRODESULFURIZATION ZONE BOILING IN THE RANGE OF ABOUT 650* TO ABOUT 1000*F.; c. feeding at least a portion of the decant oil from the catalytic cracking zone and at least a portion of the fraction from the hydrodesulfurization zone boiling above about 1,000*F. to a coking zone and coking the mixture; D. RECYCLING AT LEAST A PORTION OF THE CATALYTIC CRACKER CYCLE OIL AND THE COKER GAS OIL TO THE HYDRODESULFURIZATION ZONE; AND E. RECOVERING AS PRODUCTS OF THE INTEGRATED HYDROCARBON CONVERSION PROCESS AT LEAST GASOLINE, JET FUEL, AND COKE.
Description
United States Patent 1 1 Walkey INTEGRATED HYDROCARBON CONVERSION PROCESS [75] Inventor: John E. Walkey, Richmond, Calif. [73] Assignee: Chevron Research Company, San Francisco, Calif.
[22] Filed: June 21, 1973 [21] App]. No.: 372,117
[52] US. Cl. 208/50; 208/58; 208/89; 208/93 [51] Int. Cl Cl0g 37/06 [58] Field of Search 208/58, 89, 93, 50
[56] References Cited UNITED STATES PATENTS 2,871,182 1/1959 Weekman 208/50 3,493,489 2/1970 Naniche 208/50 3, 17,501 11/1971 Eng et a1 208/97 3,684,688 8/[972 Roselius 208/50 3,704,224 1 1/1972 Scovill et a1. 208/50 3,775,290 11/1973 Peterson ct 211...... 208/89 Primary E.raminerHerbert Levine Attorney. Agent, or Firm-G. F. Magdeburger; R. H. Davies 1111 3,891,538 [451 June 24, 1975 5 7] ABSTRACT An integrated hydrocarbon conversion process for converting a heavy hydrocarbon feedstock boiling above 650F. into various valuable products including gasoline, jet fuel, and coke, which comprises:
a. hydrodesulfurizing the feedstock hydrodesulfurization zo'ne;
b. catalytically cracking at least a portion of the fraction from the hydrodesulfurization zone boiling in the range of about 650 to about 1000F.;
c. feeding at least a portion of the decant oil from the catalytic cracking zone and at least a portion of the fraction from the hydrodesulfurization zone boiling above about 1,0000? to a coking zone and coking the mixture;
d. recycling at least a portion of the catalytic cracker cycle oil and the coker gas oil to the hydrodesulfurization zone and e. recovering as products of the integrated hydrocarbon conversion'process at least gasoline, jet fuel, and coke.
ina
2 Claims, 1 Drawing Figure a a o E CATALYTIC z CRACKING o GASOLINE ZONE 1: ATMOSPHERIC u RESIDUUM 6 M g CYCLE OIL 2 GASOLINE DECANT 011.
w (I I 4 o JET HYDRO- l;
aDESULFUR' z DlESEL p IZATION g 15 ZONE U c4 u a 650 1000 F. g a: l2 l4 0 .3 :2
0 HYDROGEN s comnc z GASOLINE zone 12 g E ,7 COKER GAS OIL COKE 1 INTEGRATED HYDROCARBON CONVERSION PROCESS BACKGROUND OF THE INVENTION A continuously rising demand for crude oil combined with a shrinking supply has created what is now being referred to in the United States as an energy crisis. In view of these conflicting developments, it is incumbent upon refiners to squeeze every last possible drop of useful product out of each barrel of crude oil. The combination of processes for the refining of heavy hydrocarbon feedstocks boiling above 650F. which will optimize the yields and selectivity of the products obtained is particularly desirable since these feedstocks, e.g., atmospheric residuum, are generally of low value and difficult to process.
The subject invention is directed to the combination of three processes in a unique manner which concurrently improves (1) product yields and product qualities from the combined processes while (2) improving the efficiency of all three processes.
SUMMARY OF THE INVENTION An integrated hydrocarbon conversion process for converting a heavy hydrocarbon feedstock boiling above 650F. into various valuable products including gasoline, jet fuel, and coke, which comprises:
a. hydrodesulfurizing the feedstock in a hydrodesulfurization zone thereby obtaining an effluent comprising gasoline, jet fuel, a fraction comprising material boiling in the range of from about 650 to about 1000F., and a fraction comprising material boiling above about l000F.;
b. catalytically cracking at least a portion of the fraction from the hydrodesulfurization zone boiling in the range of about 650 to about 1000F., thereby obtaining an effluent comprising gasoline, catalytic cracker cycle oil, and a decant oil;
c. feeding at least a portion of the decant oil and at least a portion ofthe fraction from the hydrodesulfurization zone boiling above about 1000F. to a coking zone and coking the decant oil and the fraction boiling above about I000F., thereby obtaining an effluent comprising gasoline, coker gas oil and coke;
d. recycling at least a portion of the catalytic cracker cycle oil and the coker gas oil to the hydrodesulfurization zone and hydroconverting the catalytic cracker cycle oil and coker gas oil therein; and
e. recovering as products of the integrated hydrocarbon conversion process at least gasoline, jet fuel, and coke.
BRIEF DESCRIPTION OF THE DRAWING The drawing is a schematic flow diagram of one embodiment of the process.
DETAILED DESCRIPTION OF THE INVENTION The subject invention is directed to an integrated hydrocarbon conversion process for converting heavy hydrocarbon feedstocks boiling above 650F. and containing substantial quantities of materials boiling above l000F. into various valuable products in good yield and with good selectivity for producing the more valuable products. The process of the subject invention utilizes a hydrodesulfurization zone, a catalytic cracking zone, and a coker, in a particular mode of operation which optimizes the operating efficiency of all three units.
The method of operation has been summarized above under SUMMARY OF THE INVENTION." It will be described in more detail hereinafter. Basically it calls for an integrated process combining hydrodesulfurization, catalytic cracking and coking. Products recovered using the integrated process of this invention include at least gasoline, jet fuel and coke.
Additionally, diesel fuel may be recovered as well as middle distillates for use as fuel oil. Light gases are also produced which may be handled by conventional means and used for conventional purposes.
HEAVY HYDROCARBON FEEDSTOCKS The heavy hydrocarbon feedstocks utilized in the subject invention comprise hydrocarbons boiling above about 650F. and contain substantial quantities of material boiling above I000"F. A typical feedstock is that normally produced as the residuum product from atmospheric-pressure distillation of crude oil. The initial boiling point of the feedstock can be as low as about 350F. if it is desired to hydrodesulfurize the 350 to 650F. boiling range fraction in the crude oil. Other feedstocks include heavy hydrocarbons recovered from tar sands, synthetic crude oil recovered from oil shales, heavy oils produced from liquefaction of coal, etc. The hydrocarbon feedstocks will generally contain at least about 10 percent of materials boiling above I000F.
OPERATING CONDITIONS IN THE HYDRODESULFURIZATION ZONE Hydrodesulfurization of the heavy hydrocarbon feedstock is carried out at conventional operating conditions which will generally include a temperature in the range of about 650 to about 850F., preferably within the range of from about 700 to about 800F., a liquid hourly space velocity of from about 0.1 to about 3, preferably about 0.3 to about L5, and a pressure of from about 500 to about 3,000 psig, preferably about 1,000 to about 2,000 psig.
The hydrogen supply rate (makeup and recycle hydrogen) to the hydrodesulfurization zone will generally be in the range of from about 500 to 20,000 SCF/barrel, preferably in the range from about 1,000 to about 10,000 SCF/barrel of feed, and more preferably in the range of from about 2,000 to about 4,000 SCF/barrel.
While hydrodesulfurization of the hydrocarbon feedstock fed to the hydrodesulfurization zone is the primary purpose of this zone, other reactions encompassed within the term hydroconversion, e.g., hydrogenation and hydrodenitrification, may be occurring.
HYDRODESULFURIZATION CATALYST The hydrodesulfurization catalyst utilized in the subject invention can comprise any conventional hydrodesulfurization catalyst. Normally these catalysts comprise composites comprising at least one hydrogenating component selected from Group VI metals and compounds of Group V] metals and at least one hydrogenating component selected from Group VIII metals and compounds of Group VIII metals together with a refractory support such as alumina, silica-alumina, silicaalumina-titania, and combinations of amorphous inorganic oxides with a zeolite.
A preferred hydrodesulfurization catalyst comprises a carrier of alumina in which discrete, substantially insoluble metal phosphate particles are dispersed in said carrier and consisting essentially of at least one metal phosphate selected from phosphates of the zirconium, titanium, tin, thorium, cerium and hafnium, and containing substantially the entire phosphorus content of the said catalyst. Preferred insoluble metal phosphate components are phosphates of zirconium and titanium.
The general type of insoluble metal phosphate containing catalyst and procedure for making this catalyst is disclosed in U.S. Pat. Nos. 3,546,105 and 3,493,517, both of which patents are incorporated herein by reference. As in U.S. Pat. No. 3,546,]05, substantially no silica or potentially deleterious fluorine are present in these preferred catalysts.
OPERATING CONDITIONS IN THE CATALYTIC CRACKING ZONE Operating conditions utilized in the catalytic cracking zone of the subject invention are those conventional in catalytic cracking of hydrocarbon feedstocks. These generally include a temperature in the range of from about 850 to about llF., a pressure in the range of from about 1 to about 100 psig, preferably to 30 psig. The liquid hourly space velocities within the catalytic cracking zone will generally fall within the range of from about 1.5 to about 50, although space velocities as high as I00 or more in riser cracking units may be used. Preferred temperatures for use in the catalytic cracking zone will generally fall within the range of from about 850 to about I050F.
The catalytic cracking process step including regeneration of the catalyst may be performed utilizing wellknown techniques, including, for example, fluidized bed or moving bed processes.
CATALYTIC CRACKING CATALYSTS The catalysts used in the catalytic cracking zone in the process of the present invention are those conventionally utilized in catalytic cracking processes. For example, activated, naturally occurring catalytic cracking catalysts such as clay, i.e., kaolin, can be used, as well as synthetic clays such as those disclosed in U.S. Pat. No. 3,252,889, and semi-synthetic catalysts such as silica-alumina to which kaolin has been added. Synthetically prepared cracking catalysts containing amorphous silica-alumina, with or without additional promoters, can also be used. ZeoIite-containing catalysts may also be used to reduce coke formation. Methods of preparation of the amorphous catalytic cracking catalysts are well known. The crystalline zeolitic aluminosilicate catalysts are disclosed and discussed in great detail in U.S. Pat. Nos. 3,2l0,267 and 3,27I,4l8. As is disclosed in these two prior art patents, the crystalline zeolitic molecular sieve component may have included therewith an amorphous matrix, for example, silicaalumina, titania, zirconia, magnesia, and the like.
It should be recognized that different hydrocarbon feeds present different problems and the catalyst used will, in general, be tailored to fit the particular needs of the hydrocarbon feedstock being used.
OPERATING CONDITIONS IN THE COKING ZONE The coking zone in the subject invention utilizes conventional operating techniques and conditions. Typically, it may comprise either one of two different types of coking steps; namely, delayed coking or fluid coking. These are described in detail in U.S. Pat. No. 3,493,489, the disclosure of which is hereby incorporated by reference. Additional patents including U.S. Pat Nos. 3,537,975 and 3,5l8,l82 discuss fluid coking and delayed coking, respectively.
DEFINITIONS OF TERMS The term decant oil," as used herein, means the heavy bottoms fraction of the effluent from the catalytic cracking zone. Typically it will boil in the range 800 to about I000F.
The catalytic cracking cycle oil which is recycled (at least in part) to the hydrodesulfurization may encompass both the light cycle oil typically boiling in the range 430 to 650F., and the heavy cycle oil typically boiling in the range 650 to 800F. Part of this catalytic cracker cycle oil may also be recovered for use as fuel oil.
The coker gas oil" referred to herein typically boils in the range of 400 to 900F.
The term Cf means hydrocarbons having 4 or less carbon atoms. Cf hydrocarbons recovered in fractionator 5 will be saturated. Off of fractionator 9, the C, hydrocarbon fraction will contain unsaturated hydrocarbons. Similarly, the C hydrocarbon fraction from fractionator I5 may also contain unsaturated compounds.
PROCESS OPERATION Referring now to the drawing which represents a preferred embodiment of the present invention, an atmospheric residuum boiling above 650F. is fed by line 1 to hydrodesulfurization zone 2. Hydrogen is introduced into hydrodesulfurization zone 2 via line 3. The effluent from hydrodesulfurization zone 2 is fed by line 4 to fractionator 5 where various cuts are taken off as noted in the drawing. This fractionator may consist of two stages, i.e., an atmospheric column and a vacuum column. A fraction comprising hydrocarbons boiling in the range of from 650 to l000F. is fed by line 6 to eatalytic cracking zone 7. The effluent from catalytic cracking zone 7 is fed by line 8 to fractionator 9 wherein various cuts are obtained, as indicated in the drawing. A catalytic cracking cycle oil which comprises material boiling in the range of 430 to 800F. is removed by line 10 and recycled to hydrodesulfurization zone 2. A decant oil comprising material boiling above about 800F. and primarily in the range of 800 to I000F. is removed by line I1 and sent by lines ll and 12 to coking zone 13. Additional feed to coking zone 13 comprises the material boiling above I000F. from hydrodesulfurization zone 2. This material is fed to coking zone I3 by line 12. The effluent from coking zone 13 is sent by line 14 to a fractionator 15 wherein various cuts are removed as noted in the drawing. A coker gas oil is recycled by line 16 to hydrodesulfurization zone 2. Coke is removed by line 17.
By the process described in the figure, liquid products, including gasoline, jet fuel, diesel fuel as desired, and coke are obtained in good yield and with high selectivity for the most desirable products, e.g., gasoline and jet fuel.
As is evident from the drawing, the feed to the catalytic cracking zone is desulfurized and hydrogenated in hydrodesulfurization zone 2. Rather than recycling the catalytic cracking zone cycle oil to the catalytic cracking zone as is conventionally done. the catalytic cracking cycle oil is recycled to the hydrodcsulfurization zone to improve its quality as a product and as feedstock to the catalytic cracking zone.
Rather than feeding coker gas oil to the catalytic cracking zone as is conventionally done. it is recycled to the hydrodesulfurization zone for hydrogenation to improve its quality as a catalytic cracking zone feed. Middle distillate boiling range products derived from catalytic cracking and coking are then hydrogenated in the hydrodesulfurization zone and can be drawn off as product from fractionator 5 as desired.
The benefits derived from this process and combination are derived in part from the introduction of distillate stocks. i.e., a catalytic cracking zone cycle oil and coker gas oil. into the hydrodesulfurization zone together with the hydrocarbon feedstock. From the standpoint of operating efficiency, this is more effective than utilizing separate hydrodesulfurization zones for these materials. Additionally, improved desulfurization can be obtained by combining lower boiling components. i.e.. cycle oil from the catalytic cracking zone and coker gas oil with the heavy hydrocarbon feedstock to a desulfurization zone. Further. hydrodesulfurization of the coker feed improves the yields and the quality of products from the coking zone. Similarly, the hydrogenation of coker gas oil before feeding it to a catalytic cracking zone improves its quality as catalytic cracking zone feed. Similarly, hydrogenation of the 650 to I000F. boiling range stock in the heavy hydrocarbon feed improves its quality as catalytic cracking zone feed.
ln summary, the unique integrated combination of processing steps of the subject invention provide improved feedstocks to each of the three processing zones. Improved operating efficiency results together with improved yields of high quality products.
it is apparent that many widely differing embodiments ofthis invention may be made without departing from the scope and spirit thereof; and. therefore, it is not intended to be limited except as indicated in the ap pended claims.
What is claimed is:
1. in a process wherein an atmospheric residuum hydrocarbon stock containing sulfur and substantial quantities of materials boiling above 1000F. is hydrotreated in a hydrotreating zone. a low sulfur gasoline product and a low sulfur jet fuel product are recovered from the effluent from said hydrotreating zone. a low sulfur portion of said effluent is catalytically cracked in a catalytic cracking zone; at least a portion of said effluent boiling above 1000F. is coked in a coking zone. a gasoline product is recovered from the effluent from said catalytic cracking zone. a portion of the effluent from said catalytic cracking zone is recycled to said hydrotreating zone. and a gasoline product is recovered from the effluent from said coking zone. the improved method of optimizing the operating efficiency of the combination of said hydrotreating. catalytic cracking and coking zones which comprises:
l limiting to 800F. the end point of said portion of said effluent from said catalytic cracking zone that is recycled to said hydrotreating zone;
2 passing to said coking zone and coking the portion of said effluent from said catalytic cracking zone that boils above 800F.;
3 recovering coke from said coking zone in increased yield compared with the yield if the portion of said effluent from said catalytic cracking zone boiling above 800F. were not coked in said coking zone;
4 recycling from said coking zone to said hydrotreating zone a coker gas oil in increased amount compared with the amount available for such recycle if the portion of said effluent from said catalytic cracking zone boiling above 800F. were not coked in said coking zone;
whereby there is obtained increased coke yield. increased coker gas oil for recycle to said hydrotreating zone, and improved desulfurization efficiency in said hydrotreating zone, with a resulting increased efficiency of operation of the combination of said hydrotreating, catalytic cracking and coking zones.
2. A process as in claim 1 wherein the catalyst in said hydrotreating zone comprises a Group Vl-B component, a Group VIII component, a refractory component and insoluble metal phosphate particles dispersed through said refractory component.
Claims (4)
1. IN A PROCESS WHEREIN AN ATMOSPHERIC RESIDUUM HYDROCARBON STOCK CONTAINING SULFUR AND SUBSTANTIAL QUANTITIES OF MATERIALS BOILING ABOVE 1000*F IS HYDROGENATED IN A HYDROGENATING ZONE, A LOW SULFUR GASOLINE PRODUCT AND A LOW SULFUR JET FUEL PRODUCT ARE RECOVERED FROM THE EFFLUENT IS CALYTICALLY ING ZONE, A LOW SULFUR PORTION OF SAID EFFLUENT IS CATALYTICALLY CRACKED IN A CATALYTIC CRACKING ZONE; AT LEAST A PORTION EFFLUENT BOILING ABOVE 1000*F IS COKED IN A COKING ZONE, A GASOLINE PRODUCT IS RECOVERED FROM THE EFLUENT FROM SAID CATALYTIC CRACKING ZONE, A PORTION OF THE EFFLUENT FROM SAID CATALYTIC CRACKING ZONE,IS RECYCLED TO SAID HYDROTREATING ZONE, AND A GASOLINE PRODUCT IS RECOVERED FROM THE EFFLUENT FROM SAID COKING ZONE, THE IMPROVED METHOD OF OPTIMIZING THE OPERATING EFFICIENCY OF THE COMBINATION OF SAID HYDROTREATING, CATLAYTIC CRACKIING AND COKING ZONES WHICH COMPRISES:
1. LIMITING TO 800*F, THE END POINT OF SAID PORTION OF SAID EFFLUENT FROM SAID CATALYTIC CRACKING ZONE THAT IS RECYCLED TO SAID HYDROTREATING ZONE; 2 PASSING TO SAID COKING ZONE AND COKING THE PORTION OF SAID EFFLUENT FROM SAID CATALYTIC CRACKING ZONE THAT BOILS ABOVE 800*F;
2. A process as in claim 1 wherein the catalyst in said hydrotreating zone comprises a Group VI-B component, a Group VIII component, a refractory component and insoluble metal phosphate particles dispersed through said refractory component.
3. RECOVERING COKE FROM SAID COKING ZONE IN INCREASED YIELD COMPARED WITH THE YIELD IF THE PORTION OF SAID EFFLUENT FROM SAID CATALYTIC CRACKING ZONE BOILING ABOVE 800*F WERE NOT COKED IN SAID COKING ZONE;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US372117A US3891538A (en) | 1973-06-21 | 1973-06-21 | Integrated hydrocarbon conversion process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US372117A US3891538A (en) | 1973-06-21 | 1973-06-21 | Integrated hydrocarbon conversion process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3891538A true US3891538A (en) | 1975-06-24 |
Family
ID=23466777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US372117A Expired - Lifetime US3891538A (en) | 1973-06-21 | 1973-06-21 | Integrated hydrocarbon conversion process |
Country Status (1)
| Country | Link |
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| US (1) | US3891538A (en) |
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075084A (en) * | 1977-02-17 | 1978-02-21 | Union Oil Company Of California | Manufacture of low-sulfur needle coke |
| US4302323A (en) * | 1980-05-12 | 1981-11-24 | Mobil Oil Corporation | Catalytic hydroconversion of residual stocks |
| US4325810A (en) * | 1979-10-01 | 1982-04-20 | The Standard Oil Company | Distillate yields by catalytically co-coking shale oil and petroleum residua |
| US4388175A (en) * | 1981-12-14 | 1983-06-14 | Texaco Inc. | Hydrocarbon conversion process |
| US4394250A (en) * | 1982-01-21 | 1983-07-19 | Chevron Research Company | Delayed coking process |
| US4409092A (en) * | 1980-04-07 | 1983-10-11 | Ashland Oil, Inc. | Combination process for upgrading oil products of coal, shale oil and crude oil to produce jet fuels, diesel fuels and gasoline |
| US4430207A (en) | 1983-05-17 | 1984-02-07 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4441992A (en) * | 1983-04-18 | 1984-04-10 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4457835A (en) * | 1983-09-30 | 1984-07-03 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4501653A (en) * | 1983-07-22 | 1985-02-26 | Exxon Research & Engineering Co. | Production of jet and diesel fuels |
| US4557824A (en) * | 1984-01-31 | 1985-12-10 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4604186A (en) * | 1984-06-05 | 1986-08-05 | Dm International Inc. | Process for upgrading residuums by combined donor visbreaking and coking |
| US4680105A (en) * | 1986-05-05 | 1987-07-14 | Phillips Petroleum Company | Hydrodemetallization of oils with catalysts comprising nickel phosphate and titanium phosphate |
| US4705768A (en) * | 1986-05-05 | 1987-11-10 | Phillips Petroleum Company | Coprecipitate of metal phosphates |
| US4737261A (en) * | 1984-10-05 | 1988-04-12 | International Coal Refining Company | Process for the production of premium grade needle coke from a hydrotreated SRC material |
| US4795548A (en) * | 1986-10-27 | 1989-01-03 | Intevep, S.A. | Process for making anode grade coke |
| US4832823A (en) * | 1987-04-21 | 1989-05-23 | Amoco Corporation | Coking process with decant oil addition to reduce coke yield |
| US4894144A (en) * | 1988-11-23 | 1990-01-16 | Conoco Inc. | Preparation of lower sulfur and higher sulfur cokes |
| US5167796A (en) * | 1981-06-30 | 1992-12-01 | Ucar Carbon Technology Corporation | Method of forming an electrode from a sulfur containing decant oil feedstock |
| US6171477B1 (en) * | 1997-06-10 | 2001-01-09 | Institut Francais Du Petrole | Hydroconversion of vacuum distillates and deasphalted oils in fixed beds and boiling beds |
| US6623624B2 (en) * | 2001-09-10 | 2003-09-23 | Chevron U.S.A. Inc. | Process for preparation of fuels and lubes in a single integrated hydrocracking system |
| EP2154225A1 (en) | 2008-07-23 | 2010-02-17 | Research Institute of Petroleum Industry (RIPI) | An integrated process for the conversion of heavy hydrocarbons to a light distillate and/or mid-distillate |
| WO2013093299A1 (en) | 2011-12-23 | 2013-06-27 | Total Raffinage Marketing | Recycling of a 550 °c+ cut of fcc product used to supply the fcc process |
| US8932451B2 (en) | 2011-08-31 | 2015-01-13 | Exxonmobil Research And Engineering Company | Integrated crude refining with reduced coke formation |
| US9181500B2 (en) | 2014-03-25 | 2015-11-10 | Uop Llc | Process and apparatus for recycling cracked hydrocarbons |
| US9243195B2 (en) | 2014-04-09 | 2016-01-26 | Uop Llc | Process and apparatus for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9394496B2 (en) | 2014-04-09 | 2016-07-19 | Uop Llc | Process for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9399742B2 (en) | 2014-04-09 | 2016-07-26 | Uop Llc | Process for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9422487B2 (en) | 2014-04-09 | 2016-08-23 | Uop Llc | Process for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9567537B2 (en) | 2015-03-10 | 2017-02-14 | Uop Llc | Process and apparatus for producing and recycling cracked hydrocarbons |
| US9732290B2 (en) | 2015-03-10 | 2017-08-15 | Uop Llc | Process and apparatus for cracking hydrocarbons with recycled catalyst to produce additional distillate |
| US9777229B2 (en) | 2015-03-10 | 2017-10-03 | Uop Llc | Process and apparatus for hydroprocessing and cracking hydrocarbons |
| US9783749B2 (en) | 2015-03-10 | 2017-10-10 | Uop Llc | Process and apparatus for cracking hydrocarbons with recycled catalyst to produce additional distillate |
| US9809766B2 (en) | 2015-03-10 | 2017-11-07 | Uop Llc | Process and apparatus for producing and recycling cracked hydrocarbons |
| US9840671B2 (en) | 2013-11-23 | 2017-12-12 | Indian Oil Corporation Limited | Delayed coking process |
| US9890338B2 (en) | 2015-03-10 | 2018-02-13 | Uop Llc | Process and apparatus for hydroprocessing and cracking hydrocarbons |
| US10385279B2 (en) | 2014-03-25 | 2019-08-20 | Uop Llc | Process and apparatus for recycling cracked hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2871182A (en) * | 1956-08-17 | 1959-01-27 | Socony Mobil Oil Co Inc | Hydrogenation and coking of heavy petroleum fractions |
| US3493489A (en) * | 1968-04-17 | 1970-02-03 | Chevron Res | Process for the production of jet fuel and middle distillates |
| US3617501A (en) * | 1968-09-06 | 1971-11-02 | Exxon Research Engineering Co | Integrated process for refining whole crude oil |
| US3684688A (en) * | 1971-01-21 | 1972-08-15 | Chevron Res | Heavy oil conversion |
| US3704224A (en) * | 1970-10-02 | 1972-11-28 | Standard Oil Co | Process for manufacture of improved needle coke from petroleum |
| US3775290A (en) * | 1971-06-28 | 1973-11-27 | Marathon Oil Co | Integrated hydrotreating and catalytic cracking system for refining sour crude |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2871182A (en) * | 1956-08-17 | 1959-01-27 | Socony Mobil Oil Co Inc | Hydrogenation and coking of heavy petroleum fractions |
| US3493489A (en) * | 1968-04-17 | 1970-02-03 | Chevron Res | Process for the production of jet fuel and middle distillates |
| US3617501A (en) * | 1968-09-06 | 1971-11-02 | Exxon Research Engineering Co | Integrated process for refining whole crude oil |
| US3704224A (en) * | 1970-10-02 | 1972-11-28 | Standard Oil Co | Process for manufacture of improved needle coke from petroleum |
| US3684688A (en) * | 1971-01-21 | 1972-08-15 | Chevron Res | Heavy oil conversion |
| US3775290A (en) * | 1971-06-28 | 1973-11-27 | Marathon Oil Co | Integrated hydrotreating and catalytic cracking system for refining sour crude |
Cited By (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075084A (en) * | 1977-02-17 | 1978-02-21 | Union Oil Company Of California | Manufacture of low-sulfur needle coke |
| US4325810A (en) * | 1979-10-01 | 1982-04-20 | The Standard Oil Company | Distillate yields by catalytically co-coking shale oil and petroleum residua |
| US4409092A (en) * | 1980-04-07 | 1983-10-11 | Ashland Oil, Inc. | Combination process for upgrading oil products of coal, shale oil and crude oil to produce jet fuels, diesel fuels and gasoline |
| US4302323A (en) * | 1980-05-12 | 1981-11-24 | Mobil Oil Corporation | Catalytic hydroconversion of residual stocks |
| EP0040018A3 (en) * | 1980-05-12 | 1981-12-16 | Mobil Oil Corporation | Catalytic hydroconversion of residual stocks |
| US5167796A (en) * | 1981-06-30 | 1992-12-01 | Ucar Carbon Technology Corporation | Method of forming an electrode from a sulfur containing decant oil feedstock |
| US4388175A (en) * | 1981-12-14 | 1983-06-14 | Texaco Inc. | Hydrocarbon conversion process |
| US4394250A (en) * | 1982-01-21 | 1983-07-19 | Chevron Research Company | Delayed coking process |
| US4441992A (en) * | 1983-04-18 | 1984-04-10 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4430207A (en) | 1983-05-17 | 1984-02-07 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4501653A (en) * | 1983-07-22 | 1985-02-26 | Exxon Research & Engineering Co. | Production of jet and diesel fuels |
| US4457835A (en) * | 1983-09-30 | 1984-07-03 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4557824A (en) * | 1984-01-31 | 1985-12-10 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
| US4604186A (en) * | 1984-06-05 | 1986-08-05 | Dm International Inc. | Process for upgrading residuums by combined donor visbreaking and coking |
| US4737261A (en) * | 1984-10-05 | 1988-04-12 | International Coal Refining Company | Process for the production of premium grade needle coke from a hydrotreated SRC material |
| US4705768A (en) * | 1986-05-05 | 1987-11-10 | Phillips Petroleum Company | Coprecipitate of metal phosphates |
| US4680105A (en) * | 1986-05-05 | 1987-07-14 | Phillips Petroleum Company | Hydrodemetallization of oils with catalysts comprising nickel phosphate and titanium phosphate |
| US4795548A (en) * | 1986-10-27 | 1989-01-03 | Intevep, S.A. | Process for making anode grade coke |
| US4832823A (en) * | 1987-04-21 | 1989-05-23 | Amoco Corporation | Coking process with decant oil addition to reduce coke yield |
| US4894144A (en) * | 1988-11-23 | 1990-01-16 | Conoco Inc. | Preparation of lower sulfur and higher sulfur cokes |
| EP0432335A1 (en) * | 1988-11-23 | 1991-06-19 | Conoco Inc. | Preparation of lower sulfur and higher sulfur cokes |
| US6171477B1 (en) * | 1997-06-10 | 2001-01-09 | Institut Francais Du Petrole | Hydroconversion of vacuum distillates and deasphalted oils in fixed beds and boiling beds |
| US6623624B2 (en) * | 2001-09-10 | 2003-09-23 | Chevron U.S.A. Inc. | Process for preparation of fuels and lubes in a single integrated hydrocracking system |
| SG122762A1 (en) * | 2001-09-10 | 2006-06-29 | Chevron Usa Inc | Process for preparation of fuels and lubes in a single integrated hydrocracking system |
| EP2154225A1 (en) | 2008-07-23 | 2010-02-17 | Research Institute of Petroleum Industry (RIPI) | An integrated process for the conversion of heavy hydrocarbons to a light distillate and/or mid-distillate |
| US8932451B2 (en) | 2011-08-31 | 2015-01-13 | Exxonmobil Research And Engineering Company | Integrated crude refining with reduced coke formation |
| WO2013093299A1 (en) | 2011-12-23 | 2013-06-27 | Total Raffinage Marketing | Recycling of a 550 °c+ cut of fcc product used to supply the fcc process |
| US9840671B2 (en) | 2013-11-23 | 2017-12-12 | Indian Oil Corporation Limited | Delayed coking process |
| US10385279B2 (en) | 2014-03-25 | 2019-08-20 | Uop Llc | Process and apparatus for recycling cracked hydrocarbons |
| US9181500B2 (en) | 2014-03-25 | 2015-11-10 | Uop Llc | Process and apparatus for recycling cracked hydrocarbons |
| US9243195B2 (en) | 2014-04-09 | 2016-01-26 | Uop Llc | Process and apparatus for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9394496B2 (en) | 2014-04-09 | 2016-07-19 | Uop Llc | Process for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9399742B2 (en) | 2014-04-09 | 2016-07-26 | Uop Llc | Process for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9422487B2 (en) | 2014-04-09 | 2016-08-23 | Uop Llc | Process for fluid catalytic cracking and hydrocracking hydrocarbons |
| US9732290B2 (en) | 2015-03-10 | 2017-08-15 | Uop Llc | Process and apparatus for cracking hydrocarbons with recycled catalyst to produce additional distillate |
| US9783749B2 (en) | 2015-03-10 | 2017-10-10 | Uop Llc | Process and apparatus for cracking hydrocarbons with recycled catalyst to produce additional distillate |
| US9809766B2 (en) | 2015-03-10 | 2017-11-07 | Uop Llc | Process and apparatus for producing and recycling cracked hydrocarbons |
| US9777229B2 (en) | 2015-03-10 | 2017-10-03 | Uop Llc | Process and apparatus for hydroprocessing and cracking hydrocarbons |
| US9890338B2 (en) | 2015-03-10 | 2018-02-13 | Uop Llc | Process and apparatus for hydroprocessing and cracking hydrocarbons |
| US9567537B2 (en) | 2015-03-10 | 2017-02-14 | Uop Llc | Process and apparatus for producing and recycling cracked hydrocarbons |
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