# US 11,992,830 B2 · Process for the activation and start-up of catalysts for deep hydrodesulfurization of middle distillates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,992,830 B2 - Document ID: US11992830B2 - Status: Granted - Kind: B2 - Application number: 18/128,919 - Filed: 2023-03-30 - Published: 2023-11-02 - Granted: 2024-05-28 - Earliest claimed: 2022-03-31 - Assignees: Instituto Mexicano Del Petroleo - Applicants: Instituto Mexicano del Petróleo - Inventors: Gustavo Jesús Marroquín Sánchez; Pedro Martin Vega Merino; Carlos Cureño Rodríguez; Patricia Rayo Mayoral; Salvador Castillo Cervantes; José Antonio Toledo Antonio; Jorge Ancheyta Juárez; Magally Cruz Juárez - Web page: https://patentgrep.com/patent/US11992830B2 ## CPC - B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} - C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof - B01J 37/20: Sulfiding - C10G 45/04: characterised by the catalyst used - C10G 45/22: with hydrogen dissolved or suspended in the oil - B01J 23/85: Chromium, molybdenum or tungsten - B01J 23/882: and cobalt - B01J 23/883: and nickel - B01J 2203/00: Processes utilising sub- or super atmospheric pressure - C10G 2300/1048: Middle distillates - C10G 2300/703: Activation - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - 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 The present invention deals with activation and start-up procedures of catalysts for the deep HDS of middle distillates for producing ultra low sulfur diesel (ULSD), consisting of two in situ activation stages: at stage 1, TGA is applied, and at stage 2, DMDS is used; kerosene is the transport means at these stages, which are carried out under given temperature and pressure conditions, and feedstock and hydrogen flows at established times. After the activation of the catalyst in situ, the stabilization stage takes place under selected temperature and pressure conditions, feedstock and hydrogen flow at established times, with which the stabilization of the highly dispersed metallic sulfides is achieved and, in this way, the activity of the catalysts removing contaminants for the production of ULSD is increased. ## Claims ### Claim 1 A method for the activation and start-up of catalysts for the deep hydrodesulfurization (HDS) of middle distillates, which comprises the following stages: two activation stages: stage 1, where thioglycolic acid (TGA) is applied, and stage 2, where dimethyl disulfide (DMDS) is applied; a catalyst stabilization stage, where the catalyst is stabilized; and a catalytic evaluation stage, where the activity of the catalyst is evaluated. ### Claim 2 (depends on 1) The method according to claim 1, wherein at stages 1 and 2, kerosene is used to transport TGA and DMDS. ### Claim 3 (depends on 1) The method according to claim 1, wherein at stages 1 and 2, hydrogen is fed. ### Claim 4 (depends on 1) The method according to claim 1, wherein at stage 1, the reactor temperature ranges from 200 to 230° C. ### Claim 5 (depends on 1) The method according to claim 1, wherein at stage 1, pressure ranges from 45 to 60 kg/cm2. ### Claim 6 (depends on 1) The method according to claim 1, wherein at stage 1, the Kero/TGA flow rate ranges from 170 to 190 mL/h. ### Claim 7 (depends on 1) The method according to claim 1, wherein at stage 1, the H2/oil ratio ranges from 50 to 60 m3/bbl. ### Claim 8 (depends on 1) The method according to claim 1, wherein at stage 1, time ranges from 4 to 10 h. ### Claim 9 (depends on 1) The method according to claim 1, wherein at stage 2, the temperature ranges from 200-320° C. in a staggered manner. ### Claim 10 (depends on 1) The method according to claim 1, wherein at stage 2, pressure ranges from 45 to 60 kg/cm2. ### Claim 11 (depends on 1) The method according to claim 1, wherein at stage 2, the Kero/DMDS ranges from 170 to 190 mL/h. ### Claim 12 (depends on 1) The method according to claim 1, wherein at stage 2, the H2/oil ratio ranges from 50 to 60 m3/bbl. ### Claim 13 (depends on 1) The method according to claim 1, wherein at stage 2, the time ranges from 8 to 16 h. ### Claim 14 (depends on 1) The method according to claim 1, wherein at the catalyst stabilization stage, the reactor temperature ranges from 300 to 320° C. ### Claim 15 (depends on 1) The method according to claim 1, wherein at the catalyst stabilization stage, the pressure ranges from 45 to 60 kg/cm2. ### Claim 16 (depends on 1) The method according to claim 1, wherein at the catalyst stabilization stage, the feedstock flow rate ranges from 170 to 190 mL/h. ### Claim 17 (depends on 1) The method according to claim 1, wherein at the catalyst stabilization stage, feedstocks within the interval of middle distillates can be used. ### Claim 18 (depends on 1) The method according to claim 1, wherein at the catalyst stabilization stage, the H2/oil ratio ranges from 50 to 60 m3/bbl. ### Claim 19 (depends on 1) The method according to claim 1, wherein at the catalyst stabilization stage, the time ranges from 48 to 72 h. ### Claim 20 (depends on 1) The method according to claim 1, wherein the catalytic evaluation stage comprises activity tests performed under operating conditions effective to evaluate the activity of each catalyst with every feedstock in terms of the deep HDS of middle distillates for producing ultra low sulfur diesel (ULSD), wherein the operating conditions comprise temperature, pressure conditions, liquid hourly space velocity (LHSV), and H2/oil ratio. ### Claim 21 (depends on 20) The method according to claim 20, the temperature ranges from 335 to 355° C. ### Claim 22 (depends on 20) The method according to claim 20, wherein the pressure ranges from 45 to 60 kg/cm2. ### Claim 23 (depends on 20) The method according to claim 20, wherein the LHSV ranges from 1.0 to 2.5 h−1. ### Claim 24 (depends on 20) The method according to claim 20, wherein the H2/oil ratio ranges from 50 to 60 m3/bbl. ### Claim 25 (depends on 1) The method according to claim 1, further comprising selecting operating conditions of the two activation stages, the catalyst stabilization stage, and the catalytic evaluation stage for each feedstock type and catalyst.