# US 8,980,082 B2 · Method of simultaneously removing sulfur and mercury from hydrocarbon material using catalyst by means of hydrotreating reaction

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- Number: US 8,980,082 B2
- Document ID: US8980082B2
- Status: Granted
- Kind: B2
- Application number: 13/984,412
- Filed: 2012-02-08
- Published: 2013-11-28
- Granted: 2015-03-17
- Earliest claimed: 2011-02-09
- Assignees: SK Innovation Co., Ltd.; SK Energy Co., Ltd.
- Applicants: Do Kyoung Kim; Do Woan Kim; Sang Il Lee; Seung Hoon Oh; Woo Kyung Kim; Han Seung Pan; Woo Young Kim; Kyung Soo Jun; Sun Choi
- Inventors: Do Kyoung Kim; Do Woan Kim; Sang Il Lee; Seung Hoon Oh; Woo Kyung Kim; Han Seung Pan; Woo Young Kim; Kyung Soo Jun; Sun Choi
- Web page: https://patentgrep.com/patent/US8980082B2

## CPC

- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- B01J 23/28: Molybdenum
- B01J 23/30: Tungsten
- B01J 23/75: Cobalt
- B01J 23/755: Nickel
- B01J 23/882: and cobalt
- B01J 23/883: and nickel
- B01J 23/888: Tungsten
- B01J 37/18: with gases containing free hydrogen
- B01J 37/20: Sulfiding
- C10G 25/003: {Specific sorbent material, not covered by C10G25/02 or C10G25/03}
- C10G 45/04: characterised by the catalyst used
- C10G 45/38: in combination with chromium, molybdenum or tungsten metals, or compounds thereof
- C10G 49/005: {Inhibiting corrosion in hydrotreatment processes}
- C10G 49/04: containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
- C10G 49/20: Organic compounds
- C10G 61/06: the refining step being a sorption process
- C10L 3/101: {Removal of contaminants}
- C10L 3/103: {Sulfur containing contaminants}
- B01J 21/04: Alumina
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/613: {10-100 m2/g}
- 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 35/638: {more than 1.0 ml/g}
- B01J 35/647: {2-50 nm}
- C10G 2300/1025: Natural gas
- C10G 2300/1029: Gas hydrates
- C10G 2300/104: Light gasoline having a boiling range of about 20 - 100 °C
- 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 2300/205: Metal content
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- C10G 2300/4006: Temperature
- 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
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS

## Abstract

Disclosed herein is a method of simultaneously removing sulfur and mercury from a hydrocarbon material, including: hydrotreating the hydrocarbon material containing sulfur and mercury in the presence of a catalyst including a metal supported with a carrier to convert sulfur into hydrogen sulfide, and adsorb mercury on a metal active site or a carrier of the catalyst in the form of mercury sulfide.

## Claims

### Claim 1

A method of simultaneously removing sulfur and mercury from a hydrocarbon material in a one-step reaction, the method comprising:
hydrotreating the hydrocarbon material containing sulfur and mercury in the presence of a single catalyst including a metal sulfide supported with a carrier, in which the sulfur and the mercury in the hydrocarbon material, respectively, are converted into hydrogen sulfide and metal mercury, and the converted metal mercury reacts with active sites of the metal sulfide in one of the single catalyst or the converted hydrogen sulfide to form mercury sulfide, and the formed mercury sulfide is absorbed on the active sites of one of the metal sulfide or the carrier of the single catalyst,
wherein the metal sulfide in the single catalyst is at least one selected from the group consisting of cobalt, molybdenum, nickel, tungsten, cobalt-molybdenum, nickel-molybdenum, nickel-tungsten, and cobalt-tungsten, and
wherein the hydrotreating reaction is conducted at about 270-400° C.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the hydrocarbon material is at least one selected from the group consisting of crude oil, natural gas and natural gas condensate; and gas, light naphtha, heavy naphtha, kerosene, light gas oil (LGO), heavy gas oil (HGO) and atmospheric oil residue produced therefrom.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the hydrocarbon material is heavy naphtha having a boiling point of 60° C.˜180° C.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the carrier is at least one selected from the group consisting of alumina, active carbon, silica, silica-alumina, zirconia, and titania.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the hydrotreating reaction is conducted on a condition of a temperature of 270-36° C. a hydrogen pressure of 25-90 kg/cm2, a liquid space velocity of 0.3-12 hr−1, and a flow rate of hydrogen per unit volume of the single catalyst of 5-500 vol/hr.

### Claim 6 (depends on 1)

The method according to claim 1, further comprising:
adding a sulfur compound to the hydrocarbon material.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the sulfur compound is represented by the following Formula:
R1—(S)x—R2
wherein X is an integer of 1˜7, and R1 and R2 are each independently at least one selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl and aryl.

### Claim 8 (depends on 6)

The method according to claim 6, wherein the sulfur compound is at least one selected from the group consisting of hydrogen sulfide, dimethylsulfide (DMS), dimethyldisulfide (DMDS), diethylsulfide (DES), diethyldisulfide (DEDS), and sour gas.

### Claim 9 (depends on 6)

The method according to claim 6, wherein an amount of the sulfur compound added to the hydrocarbon material is 1 mg˜10000 mg per 1 kg of the hydrocarbon material, based on sulfur atoms.

### Claim 10 (depends on 6)

The method according to claim 6, wherein an amount of the sulfur compound added to the hydrocarbon material is 1 mg˜3000 mg per 1 kg of the hydrocarbon material, based on sulfur atoms.

### Claim 11 (depends on 1)

The method according to claim 1, wherein an adsorbing material is further provided at a rear end of a reactor including the single catalyst.

### Claim 12 (depends on 11)

The method according to claim 11, wherein the adsorbing material is at least one selected from the group consisting of alumina, active carbon, silica, silica-alumina, zirconia, and titania.