# US 2019/0375995 A1 · Naphtha hydrodesulfurization

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- Number: US 2019/0375995 A1
- Document ID: US20190375995A1
- Status: Published application
- Kind: A1
- Application number: 16/415,033
- Filed: 2019-05-17
- Published: 2019-12-12
- Earliest claimed: 2018-06-07
- Assignees: ExxonMobil Research and Engineering Company
- Applicants: ExxonMobil Research and Engineering Company
- Inventors: Chuansheng Bai; Majosefina Cunningham; Gregory R. Johnson; Wenyih F. Lai; Brandon J. O'Neill
- Web page: https://patentgrep.com/patent/US20190375995A1

## CPC

- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- C10G 45/12: containing crystalline alumino-silicates, e.g. molecular sieves
- B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J 29/46: Iron group metals or copper
- B01J 29/48: containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 29/703: {MRE-type, e.g. ZSM-48}
- B01J 29/7261: {MRE-type, e.g. ZSM-48}
- B01J 35/615: {100-500 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 37/0201: {Impregnation}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/20: Sulfiding
- B01J 21/04: Alumina
- B01J 21/08: Silica
- B01J 23/882: and cobalt
- B01J 2229/42: Addition of matrix or binder particles
- B01J 2229/60: Synthesis on support
- C10G 2300/1044: Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2400/02: Gasoline
- 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

Methods are provided for performing selective hydrodesulfurization on a naphtha boiling range stream naphtha boiling range portion of a feed. It has been unexpectedly discovered that hydrodesulfurization with improved octane retention can be performed by using a catalyst that comprises CoMo supported on a catalyst support that includes a zeotype framework. By using a catalyst support including a zeotype framework, an unexpectedly high amount of octane in the naphtha boiling range portion of the hydrodesulfurized effluent is maintained.

## Claims

### Claim 1

A method for performing naphtha hydrodesulfurization, comprising:
sulfiding a hydrotreating catalyst comprising 1.5 wt % to 4.0 wt % cobalt oxide and 5.0 wt % to 15 wt % molybdenum oxide, relative to a weight of the hydrotreating catalyst, an organic dispersion agent, and a support comprising a zeotype framework having a 10-member ring pore channel as the largest size pore channel, to form a sulfided hydrotreating catalyst; and
exposing a feed comprising a naphtha boiling range portion to the sulfided hydrotreating catalyst under selective hydrodesulfurization conditions to form a hydrotreated effluent, the naphtha boiling range portion of the feed comprising 5.0 wt % or more of olefins.

### Claim 2 (depends on 1)

The method of claim 1, wherein the support comprises a MEL framework, a MRE framework, or a combination thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein the support comprises ZSM-11, ZSM-48, or a combination thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the support further comprises a binder.

### Claim 5 (depends on 4)

The method of claim 4, wherein the binder comprises alumina, silica, titania, zirconia, or a combination thereof.

### Claim 6 (depends on 4)

The method of claim 4, wherein the support comprises a weight ratio of zeotype framework to binder of 0.2 to 10.

### Claim 7 (depends on 1)

The method of claim 1, wherein the hydrotreating catalyst comprises an average pore size of 17.0 nm or less.

### Claim 8 (depends on 1)

The method of claim 1, wherein the hydrotreating catalyst comprises 5.0 wt % to 12 wt % molybdenum oxide.

### Claim 9 (depends on 1)

The method of claim 1, wherein the naphtha boiling range portion of the feed comprises a naphtha boiling range portion of a fluid catalytic cracking effluent, a steam cracker effluent, a coker effluent, or a combination thereof.

### Claim 10 (depends on 1)

The method of claim 1, wherein the sulfidation is performed in-situ.

### Claim 11 (depends on 1)

The method of claim 1, wherein the sulfidation is performed ex-situ.

### Claim 12 (depends on 1)

The method of claim 1, wherein the naphtha boiling range portion of the feed comprises 300 wppm to 7000 wppm of sulfur.

### Claim 13 (depends on 1)

The method of claim 1, wherein the selective hydrodesulfurization conditions are effective for reducing the sulfur content of the naphtha boiling range portion of the hydrotreated effluent to 100 wppm or less, or wherein the selective hydrodesulfurization conditions are effective for performing 92% to 98% desulfurization of the naphtha boiling range portion of the feed, or a combination thereof.

### Claim 14 (depends on 1)

The method of claim 1 wherein the selective hydrodesulfurization conditions comprise a temperature of 150° C. to 400° C., a hydrogen partial pressure of 0.4 MPa-g to 14.0 MPa-g, a liquid hourly space velocity of 0.1 hr−1 to 12 hr−1, and a hydrogen treat gas rate of 89 m3/m3 to 890 m3/m3.

### Claim 15 (depends on 1)

The method of claim 1, wherein the feed comprises a T5 distillation point of 35° C. or more and a T95 distillation point of 232° C. or less, or wherein the naphtha boiling range portion of the feed comprises an initial distillation point of 35° C. or more and a final distillation point of 232° C. or less, or a combination thereof.

### Claim 16 (depends on 1)

The method of claim 1, wherein the organic dispersion agent contains oxygen atoms, nitrogen atoms or both.

### Claim 17 (depends on 1)

The method of claim 1, wherein the organic dispersion agent comprises a mono-dentate ligand, a bi-dentate ligand, a poly-dentate ligand, or a combination thereof.

### Claim 18 (depends on 17)

The method of claim 17, wherein the organic dispersion agent comprises at least one carboxylic acid, polyol, amino acid, amine, amide, amino alcohol, ketone or ester.

### Claim 19 (depends on 17)

The method of claim 17, wherein the organic dispersion agent is a chelating agent.

### Claim 20 (depends on 1)

The method of claim 1, wherein the organic dispersion agent comprises at least one of phenanthroline, quinolinol, salicylic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CYDTA), alanine, arginine, triethanolamine (TEA), glycerol, histidine, acetylacetonate, guanidine, nitrilotriacetic acid (NTA), citric acid or urea.