# US 10,370,604 B2 · Process for simultaneous removal of arsenic and sulphur from hydrocarbon streams

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- Number: US 10,370,604 B2
- Document ID: US10370604B2
- Status: Granted
- Kind: B2
- Application number: 15/717,009
- Filed: 2017-09-27
- Published: 2018-03-29
- Granted: 2019-08-06
- Earliest claimed: 2016-09-29
- Assignees: Petroleo Brasileiro S.A. - Petrobras
- Applicants: Petroleo Brasileiro S.A.—Petrobras
- Inventors: Wladmir Ferraz De Souza; Marcus Vinicius Eiffle Duarte; Lilian Ernst; Carmen Lucia Tavares Da Silva
- Web page: https://patentgrep.com/patent/US10370604B2

## CPC

- C10G 70/046: {by adsorption, i.e. with the use of solids}
- B01D 53/48: Sulfur compounds
- B01D 53/64: Heavy metals or compounds thereof, e.g. mercury
- B01J 20/0229: {Compounds of Fe}
- B01J 20/3028: {Granulating, agglomerating or aggregating}
- B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing}
- C01G 49/02: Oxides; Hydroxides {(C01G49/0018 takes precedence)}
- C07C 7/1485: {oxides; hydroxides; salts (C07C7/156 takes precedence)}
- C10G 25/003: {Specific sorbent material, not covered by C10G25/02 or C10G25/03}
- C10G 31/06: by heating, cooling, or pressure treatment
- B01D 2253/1124: Metal oxides
- B01D 2256/24: Hydrocarbons
- B01D 2257/306: Organic sulfur compounds, e.g. mercaptans
- B01D 2257/60: Heavy metals or heavy metal compounds
- B01J 2220/42: Materials comprising a mixture of inorganic materials (materials coated or impregnated on a carrier B01J20/32)
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- 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
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The present invention describes a process for the simultaneous removal of arsenic and sulphur compounds from hydrocarbon streams of fossil origin, wherein hydrocarbon streams of fossil origin resulting from the retorting process of schist are purified by direct contact with hydrated iron oxide, such as goethite (α-FeOOH) in its raw natural form (limonite ore particles).

## Claims

### Claim 1

A process for simultaneous removal of arsenic and sulphur from hydrocarbon streams, comprising the steps of
a) grinding schist rock contaminated with arsenic and sulphur to obtain particles of schist rock;
b) removing the arsenic and sulphur from the particles of schist rock by
b1) mixing the particles of schist rock with particles of hydrated iron oxide (FeOOH) in a schist:FeOOH ratio, by weight, in the range from 100:1 to 1:100 and
b2) pyrolyzing the mixture obtained in step b1) with heating from ambient temperature to a temperature in the range 400-600° C.,
wherein the process takes place in the absence of hydrogen partial pressure and at atmospheric pressure.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the particles of schist rock are ground to a granulometry in the range between 3.5 and 20 Tyler mesh.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the particles of schist rock are mixed with particles of FeOOH in a schist:FeOOH ratio, by weight, in the range from 1:1 to 50:1.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the particles of hydrated iron oxide (FeOOH) are particles of goethite (α-FeOOH) in the natural form of limonite ore.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the pyrolyzing step b2) is carried out with heating from ambient temperature to a temperature of 500° C.

### Claim 6 (depends on 1)

The process according to claim 1, wherein arsenic compounds selected from the group consisting of organic compounds of As(III) and As(V) are removed.

### Claim 7 (depends on 1)

The process according to claim 1, wherein mercaptides are removed.

### Claim 8

A process for simultaneous removal of arsenic and sulphur from hydrocarbon streams, comprising the steps of
a) extruding paste of limonite ore particles, followed by drying; and
b) removing arsenic and sulphur from a hydrocarbon stream contaminated with arsenic and sulphur by passing the hydrocarbon stream through the bed obtained in a) at a temperature of at least 80° C., varying up to 420° C.,
wherein the process takes place in the absence of hydrogen partial pressure and at atmospheric pressure.

### Claim 9 (depends on 8)

The process according to claim 8, wherein extrusion of particles of natural limonite and drying at 120° C., for 3 hours, are carried out in a N2 stream.

### Claim 10 (depends on 8)

The process according to claim 8, wherein hydrocarbon streams of fossil origin are treated, selected from the group consisting of: hydrocarbon streams resulting from the industrial retorting process of schist rock; gaseous streams of light hydrocarbons; gaseous or liquid hydrocarbon streams derived from petroleum or from coal.

### Claim 11 (depends on 10)

The process according to claim 10, wherein the hydrocarbon stream of fossil origin is a hydrocarbon stream resulting from the industrial retorting process of schist rock and is selected from shale oil and the distilled derivatives thereof.

### Claim 12 (depends on 10)

The process according to claim 10, wherein the hydrocarbon stream of fossil origin is a gaseous stream of light hydrocarbons and is shale gas resulting from processes of fracturing in subsoils.

### Claim 13 (depends on 8)

The process according to claim 8, wherein arsenic compounds selected from the group consisting of organic compounds of As(III) and As(V) are removed.

### Claim 14 (depends on 8)

The process according to claim 8, wherein mercaptides are removed.