# US 2012/0074042 A1 · Process for reducing the total acid number of a hydrocarbon feed

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- Number: US 2012/0074042 A1
- Document ID: US20120074042A1
- Status: Published application
- Kind: A1
- Application number: 12/889,715
- Filed: 2010-09-24
- Published: 2012-03-29
- Earliest claimed: 2010-09-24
- Assignees: Chevron U.S.A. Inc.
- Inventors: Shabbir Husain; Lin Li; Zhen Zhou; Alexander E. Kuperman; Zunqing He; Huping Luo
- Web page: https://patentgrep.com/patent/US20120074042A1

## CPC

- C10G 29/00: Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G 29/04: Metals, or metals deposited on a carrier
- C10G 29/06: Metal salts, or metal salts deposited on a carrier
- C10G 2300/1011: Biomass
- C10G 2300/1033: Oil well production fluids
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G 2300/1074: Vacuum distillates
- C10G 2300/1077: Vacuum residues
- C10G 2300/203: Naphthenic acids, TAN
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- Y02P 30/20: using bio-feedstock
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed are embodiments relating to a process for reducing the total acid number of a hydrocarbon feed by contacting the feed with a metal titanate catalyst having an MTiO3 structure wherein M is a metal having a valence of 2+, resulting in a hydrocarbon product having a final total acid number lower than the initial total acid number of the feed. The process is useful for pretreating high acid crudes prior to further processing thus avoiding corrosion of equipment used in refining operations. The process can be integrated into conventional refining operations in order to treat various refinery streams. In one embodiment, a process is provided for refining a low acid crude oil and a high acid crude oil by separately introducing a relatively low acid crude oil feed and a relatively high acid crude oil feed to an atmospheric distillation column, wherein the relatively high acid crude oil feed is contacted with a metal titanate catalyst prior to introduction to the atmospheric distillation column.

## Claims

### Claim 1

A process for reducing the total acid number of a liquid hydrocarbon feed, comprising contacting a liquid hydrocarbon feed having an initial total acid number of at least 0.5 with a catalyst comprising a metal titanate having an MTiO3 structure, wherein M is a metal having a valence of 2+ at a temperature of between 200° C. and 400° C., thereby resulting in a treated hydrocarbon product having a final total acid number at least 10% lower than the initial total acid number.

### Claim 2 (depends on 1)

The process of claim 1, wherein the catalyst further comprises a metal oxide.

### Claim 3 (depends on 1)

The process of claim 1, wherein the final total acid number is at least 50% lower than the initial total acid number.

### Claim 4 (depends on 1)

The process of claim 1, wherein the final total acid number is at least 90% lower than the initial total acid number.

### Claim 5 (depends on 1)

The process of claim 1, wherein the catalyst comprises at least 1% by weight metal titanate.

### Claim 6 (depends on 1)

The process of claim 1, wherein the catalyst comprises at least 5% by weight metal titanate.

### Claim 7 (depends on 1)

The process of claim 1, wherein the catalyst comprises at least 10% by weight metal titanate.

### Claim 8 (depends on 1)

The process of claim 1, wherein the catalyst comprises at least 80% by weight metal titanate.

### Claim 9 (depends on 1)

The process of claim 1, wherein the catalyst consists essentially of a metal titanate having an MTiO3 structure, with M being a metal having a valence of 2+.

### Claim 10 (depends on 9)

The process of claim 9, wherein the catalyst consists essentially of a basic oxide and a metal titanate having an MTiO3 structure, with M being a metal having a valence of 2+, wherein the molar ratio of the basic oxide to the metal titanate ranges from 1:10 to 10:1.

### Claim 11 (depends on 10)

The process of claim 10, wherein the basic oxide is selected from the group of calcium oxide, magnesium oxide, magnesium aluminum oxide, zinc oxide, lanthanum oxide, cerium oxide, barium oxide and mixtures thereof.

### Claim 12 (depends on 1)

The process of claim 1, wherein the catalyst further comprises a support selected from the group consisting of silica, alumina, silica-alumina, carbon, molecular sieves and mixtures thereof.

### Claim 13 (depends on 1)

The process of claim 1, wherein the hydrocarbon feed is contacted with the catalyst at a temperature of between 200° C. and 350° C.

### Claim 14 (depends on 1)

The process of claim 1, wherein the catalyst comprises a metal titanate selected from the group consisting of magnesium titanate, copper titanate, nickel titanate, iron(II) titanium oxide, cobalt titanium oxide, manganese(II) titanium oxide, lead(II) titanate, calcium titanate, barium titanate and zinc titanate.

### Claim 15 (depends on 1)

The process of claim 1, wherein the catalyst comprises a metal titanate selected from the group consisting of calcium titanate, barium titanate and zinc titanate.

### Claim 16 (depends on 1)

The process of claim 1, wherein the catalyst consists essentially of a metal titanate selected from the group consisting of magnesium titanate, copper titanate, nickel titanate, iron(II) titanium oxide, cobalt titanium oxide, manganese(II) titanium oxide, lead(II) titanate, calcium titanate, barium titanate and zinc titanate.

### Claim 17 (depends on 1)

The process of claim 1, wherein the hydrocarbon feed is contacted with the catalyst at a LHSV of between 0.1 and 10 h−1.

### Claim 18 (depends on 1)

The process of claim 1, wherein the hydrocarbon feed is contacted with the catalyst at a LHSV of between 0.4 and 2 h−1.

### Claim 19 (depends on 1)

The process of claim 1, wherein the hydrocarbon feed is contacted with the catalyst in a fixed bed reactor.

### Claim 20 (depends on 1)

The process of claim 1, wherein the hydrocarbon feed is contacted with the catalyst in a slurry bed reactor.

### Claim 21 (depends on 1)

The process of claim 1, wherein the hydrocarbon feed is selected from the group consisting of crude oil, synthetic crude, distillate products, straight run feed, atmospheric and vacuum bottoms, vacuum gas oil and biologically derived oils.

### Claim 22 (depends on 1)

The process of claim 1, further comprising introducing a stripping gas stream capable of degassing the reactor contents.

### Claim 23 (depends on 1)

The process of claim 1, wherein the hydrocarbon feed is contacted with the catalyst without the addition of hydrogen gas.

### Claim 24 (depends on 1)

The process of claim 1, wherein the treated hydrocarbon product is used as feed for an atmospheric distillation process.

### Claim 25 (depends on 1)

The process of claim 1, wherein the treated hydrocarbon product is used as feed for a downstream FCC unit.

### Claim 26 (depends on 1)

The process of claim 1, wherein the treated hydrocarbon product is used as feed for a downstream hydroprocessing unit.

### Claim 27 (depends on 1)

The process of claim 1, wherein the liquid hydrocarbon feed has an initial acid number of at least 10, and wherein the final total acid number is at least 50% lower than the initial total acid number.

### Claim 28 (depends on 1)

The process of claim 1, wherein the metal titanate has a perovskite structure.

### Claim 29

A process for refining a low acid crude oil and a high acid crude oil comprising separately introducing a relatively low acid crude oil feed and a relatively high acid crude oil feed to an atmospheric distillation column, wherein the relatively high acid crude oil feed is contacted with a catalyst comprising a metal titanate having an MTiO3 structure, wherein M is a metal having a valence of 2+ prior to introduction to the atmospheric distillation column.