# US 5,346,609 A · Hydrocarbon upgrading process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,346,609 A - Document ID: US5346609A - Status: Granted - Kind: A - Application number: 07/745,311 - Filed: 1991-08-15 - Granted: 1994-09-13 - Earliest claimed: 1991-08-15 - Assignees: Mobil Oil Corporation - Inventors: David L. Fletcher; Michael S. Sarli; Stuart S. Shih - Web page: https://patentgrep.com/patent/US5346609A ## CPC - C10G 69/08: including at least one step of reforming naphtha - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES ## Abstract A process for producing a desulfurized gasoline boiling range product of relatively high octane number from a sulfur containing feed boiling in the naphtha boiling range by converting the feed in a first stage over a conventional hydrodesulfurization catalyst, and then converting at least the normally liquid portion of the product of this first stage conversion over a catalyst comprising a zeolitic behaving refractory solid having acid activity and shape selectivity to produce a product having a sulfur content within the required specifications, and an octane number which at least approaches the octane number of the feed. ## Claims ### Claim 1 A process of upgrading a sulfur containing hydrocarbon comprising a catalytically cracked naphtha feed fraction comprising olefins and boiling in the gasoline boiling range, the feed fraction being selected from a naphtha having a boiling range in the range of C.sub.6 to 330.degree. F., a naphtha having a boiling range in the range of C.sub.5 to 420.degree. F., a naphtha having a boiling range in the range of 260.degree. to 412.degree. F. or a naphtha boiling in the range of 330.degree. to 500.degree. F., which comprises: contacting such sulfur containing naphtha feed fraction with a hydrodesulfurization catalyst in a first reaction zone, operating under a combination of elevated temperature, elevated pressure and an atmosphere comprising hydrogen, such as to produce a first intermediate reaction zone product comprising a normally liquid fraction which has a reduced sulfur content and a reduced octane number as compared to the feed; cascading the first intermediate reaction zone product to a second reaction zone and contacting the first intermediate product in the second reaction zone in the presence of hydrogen with a different catalyst, comprising a zeolitic behaving refractory solid having an acid activity equivalent to at least about 20 alpha, and a topology such that, in the aluminosilicate form, it would have a constraint index of 2 to 12; under a combination of conditions comprising elevated temperature of from 700.degree. to 800.degree. F., sufficient to convert said first intermediate product fraction boiling in the gasoline boiling range to a product comprising a fraction boiling in the gasoline boiling range having a higher octane number than said first intermediate gasoline boiling range fraction; and recovering at least said upgraded gasoline boiling range product fraction. ### Claim 2 (depends on 1) The process as claimed in claim 1 wherein said feed fraction comprises a light naphtha fraction having a boiling range within the range of C.sub.6 to 330.degree. F. ### Claim 3 (depends on 1) The process as claimed in claim 1 wherein said feed fraction comprises a full range naphtha fraction having a boiling range within the range of C.sub.5 to 420.degree. F. ### Claim 4 (depends on 1) The process as claimed in claim 1 wherein said feed fraction comprises a heavy naphtha fraction having a boiling range within the range of 330.degree. to 500.degree. F. ### Claim 5 (depends on 1) The process as claimed in claim 1 wherein said feed fraction comprises a heavy naphtha fraction having a boiling range within the range of 330.degree. to 412.degree. F. ### Claim 6 (depends on 1) The process as claimed in claim 1 wherein said different catalyst in said second reaction zone comprises a zeolite behaving refractory solid having a topology substantially corresponding to the topology of at least one member of the group consisting of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-50, and MCM-22. ### Claim 7 (depends on 6) The process as claimed in claim 6 wherein said different catalyst comprises a zeolite behaving refractory solid having a topology substantially corresponding to the topology of ZSM-5 in an aluminosilicate form. ### Claim 8 (depends on 1) The process as claimed in claim 1 wherein said different catalyst comprises said zeolite behaving refractory solid in combination with a binder. ### Claim 9 (depends on 8) The process as claimed in claim 8 wherein said binder is at least one member selected from the group consisting of silica, alumina, silica-alumina, silica-zirconia, and silica-titania. ### Claim 10 (depends on 1) The process as claimed in claim 1 wherein said hydrodesulfurization catalyst comprises a group VIII metal. ### Claim 11 (depends on 10) The process as claimed in claim 10 wherein said hydrodesulfurization catalyst comprises a group VIII and a group VI metal. ### Claim 12 (depends on 1) The process as claimed in claim 1 wherein said hydrodesulfurization catalyst comprises cobalt and molybdenum carried on an alumina substrate. ### Claim 13 (depends on 1) The process as claimed in claim 1 wherein said hydrodesulfurization is carried out at a temperature of about 400.degree. to 800.degree. F., a pressure of about 50 to 1500 psig, a space velocity of about 0.5 to 10 LHSV, and a hydrogen to hydrocarbon ratio of about 500 to 5000 standard cubic feet of hydrogen per barrel of feed. ### Claim 14 (depends on 1) The process as claimed in claim 1 wherein said hydrodesulfurization is carried out at a temperature of about 500.degree. to 750.degree. F., a pressure of about 300 to 1000 psig, a space velocity of about 1 to 6 LHSV, and a hydrogen to hydrocarbon ratio of about 1000 to 2500 standard cubic feet of hydrogen per barrel of feed. ### Claim 15 (depends on 1) The process as claimed in claim 1 wherein the second stage upgrading is carried out at a temperature of about 700.degree. to 900.degree. F., a pressure of about 50 to 1500 psig, a space velocity of about 0.5 to 10 LHSV, and a hydrogen to hydrocarbon ratio of about 0 to 5000 standard cubic feet of hydrogen per barrel of feed. ### Claim 16 (depends on 1) The process as claimed in claim 1 wherein the second stage upgrading is carried out at a temperature of about 700.degree. to 800.degree. F., a pressure of about 300 to 1000 psig, a space velocity of about 1 to 6 LHSV, and a hydrogen to hydrocarbon ratio of about 100 to 2500 standard cubic feet of hydrogen per barrel of feed. ### Claim 17 (depends on 1) The process as claimed in claim 1 including additionally recovering from said second stage product, a normally gaseous fraction boiling below C.sub.5, and alkylating at least the C.sub.4 unsaturated portion thereof into a normally liquid hydrocarbonaceous product having a high octane number and boiling in the gasoline boiling range. ### Claim 18 (depends on 17) The process as claimed in claim 17 including blending said alkylate with said upgraded gasoline boiling range fraction.