# US 10,246,649 B2 · Process for reducing the total acid number in refinery feedstocks > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,246,649 B2 - Document ID: US10246649B2 - Status: Granted - Kind: B2 - Application number: 15/497,920 - Filed: 2017-04-26 - Published: 2017-08-10 - Granted: 2019-04-02 - Earliest claimed: 2011-07-29 - Assignees: Saudi Arabian Oil Company - Applicants: Saudi Arabian Oil Company - Inventors: Omer Refa Koseoglu; Adnan Al-Hajji; Hendrik Muller; Hanadi Al Jawad - Web page: https://patentgrep.com/patent/US10246649B2 ## CPC - C10G 29/16: Metal oxides - B01J 21/04: Alumina - B01J 21/10: Magnesium; Oxides or hydroxides thereof - B01J 23/007: {Mixed salts} - B01J 23/06: of zinc, cadmium or mercury - B01J 27/236: Hydroxy carbonates - B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)} - C10G 19/02: with aqueous alkaline solutions - C10G 25/003: {Specific sorbent material, not covered by C10G25/02 or C10G25/03} - C10G 2300/203: Naphthenic acids, TAN - C10G 2300/4006: Temperature - C10G 2300/4012: Pressure - C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV - C10G 2300/80: Additives - 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 - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract A process is described for reducing the total acid number of a refinery feedstock. A refinery feedstock containing naphthenic acids is contacted with an effective amount of solid catalyst that has been pretreated with an aqueous caustic base, for a period of time sufficient to neutralize at least a portion of the naphthenic acids in the feedstock. Thereafter, the aqueous phase is separated from the neutralized refinery feedstock. ## Claims ### Claim 1 A process for reducing the total acid number of a refinery feedstock containing naphthenic acids, the process comprising contacting the refinery feedstock containing naphthenic acids with an effective amount of solid catalyst that has been pretreated with a caustic base for a period of time sufficient and at a temperature of at least 200 C to neutralize at least a portion of the naphthenic acids in the refinery feedstock to produce a treated product having reduced total acid number. ### Claim 2 (depends on 1) The process of claim 1, which further includes adding an emulsion breaking additive to the treated mixture to minimize emulsion formation. ### Claim 3 (depends on 2) The process of claim 2, wherein the emulsion breaking additive is triethanolamine, ethoxylated phenol resins, zinc chloride, or polymerized trithionylamine. ### Claim 4 (depends on 1) The process of claim 1, wherein the solid catalyst is a single or a group of catalysts which exhibit basic properties. ### Claim 5 (depends on 1) The process of claim 1, wherein the solid catalyst comprises at least one metal oxide including one or more materials selected from the group consisting of zinc oxide, aluminum oxide, zinc aluminates, and layered double hydroxides including magnesium/aluminum. ### Claim 6 (depends on 1) The process of claim 1, wherein the refinery feedstock contains carboxylic acids. ### Claim 7 (depends on 1) The process of claim 1, wherein the caustic base is sodium hydroxide or potassium hydroxide. ### Claim 8 (depends on 1) The process of claim 1, wherein the refinery feedstock is supplied with a liquid hourly space velocity in the range of from 0.1 to 10 h−1. ### Claim 9 (depends on 1) The process of claim 1, wherein the refinery feedstock is supplied with a liquid hourly space velocity in the range of from 0.5 to 4 h−4. ### Claim 10 (depends on 1) The process of claim 1, wherein the refinery feedstock is supplied with a liquid hourly space velocity in the range of from 1 to 2 h−4. ### Claim 11 (depends on 1) The process of claim 1, wherein the neutralization reaction is conducted at a temperature in the range of from 200 to 600° C. ### Claim 12 (depends on 1) The process of claim 1, wherein neutralization reaction is conducted at a temperature in the range of from 300 to 400° C. ### Claim 13 (depends on 1) The process of claim 1, wherein neutralization reaction is conducted at a temperature in the range of from 300 to 350° C. ### Claim 14 (depends on 1) The process of claim 1, wherein neutralization reaction is conducted at a pressure in the range of from 1 to 20 Kg/cm2. ### Claim 15 (depends on 1) The process of claim 1, wherein neutralization reaction is conducted at a pressure in the range of from 1 to 10 Kg/cm2. ### Claim 16 (depends on 14) The process of claim 14, wherein the pressure is maintained by refinery feedstock pressure alone, without any supply of added overhead or blanketing gas. ### Claim 17 (depends on 1) The process of claim 1, wherein the pretreatment of the solid catalyst is carried out in situ in a neutralization vessel used for contacting the refinery feedstock by, before contacting the refinery feedstock, loading the solid catalyst in the neutralization vessel, passing the caustic base at a temperature and for a period of time effective for pretreatment, and then contacting the refinery feedstock with the solid catalyst that has been pretreated to neutralize naphthenic acids in the refinery feedstock. ### Claim 18 (depends on 1) The process of claim 1, wherein the pretreatment of the solid catalyst is carried out ex situ in a by contacting the solid catalyst in a separate vessel with the caustic base at a temperature and for a period of time effective for pretreatment, and loading the solid catalyst that has been pretreated into a separate vessel for contacting the refinery feedstock with the solid catalyst that has been pretreated to neutralize naphthenic acids in the refinery feedstock. ### Claim 19 (depends on 18) The process of claim 18, wherein the separate vessel for pretreatment of the solid catalyst is a batch vessel or a continuous tubular vessel. ### Claim 20 (depends on 1) The process of claim 1, wherein the solid catalyst comprises zinc oxide. ### Claim 21 (depends on 1) The process of claim 1, wherein the solid catalyst comprises aluminum oxide. ### Claim 22 (depends on 1) The process of claim 1, wherein the solid catalyst comprises zinc aluminates. ### Claim 23 (depends on 1) The process of claim 1, wherein the solid catalyst comprises layered double hydroxides including magnesium/aluminum. ### Claim 24 (depends on 1) The process of claim 1, wherein the solid catalyst comprises at least one metal oxide including one or more materials selected from the group consisting of zinc oxide, zinc aluminates, and layered double hydroxides including magnesium/aluminum.