# US 7,744,841 B2 · Sulfur removal using ferrous carbonate absorbent

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 7,744,841 B2
- Document ID: US7744841B2
- Status: Granted
- Kind: B2
- Application number: 11/228,713
- Filed: 2005-09-15
- Published: 2007-03-15
- Granted: 2010-06-29
- Earliest claimed: 2005-09-15
- Assignees: New Technology Ventures, Inc.
- Inventors: Floyd E. Farha
- Web page: https://patentgrep.com/patent/US7744841B2

## CPC

- C04B 28/06: Aluminous cements (monolithic refractories or refractory mortars C04B35/66)
- B01D 15/00: Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D 53/485: {containing only one sulfur compound other than sulfur oxides or hydrogen sulfide}
- B01D 53/52: Hydrogen sulfide
- B01J 20/0229: {Compounds of Fe}
- B01J 20/0277: {Carbonates of compounds other than those provided for in B01J20/043}
- B01J 20/28004: {Sorbent size or size distribution, e.g. particle size}
- B01J 20/28014: {characterised by their form}
- B01J 20/28019: {Spherical, ellipsoidal or cylindrical}
- B01J 20/2803: {Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products}
- B01J 20/3007: {Moulding, shaping or extruding}
- B01J 20/3028: {Granulating, agglomerating or aggregating}
- B01J 20/3042: {Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent}
- C10G 25/003: {Specific sorbent material, not covered by C10G25/02 or C10G25/03}
- C10L 3/10: Working-up natural gas or synthetic natural gas
- C10L 3/102: {of acid contaminants}
- B01D 2251/606: Carbonates
- B01D 2257/306: Organic sulfur compounds, e.g. mercaptans
- B01D 2257/308: Carbonoxysulfide COS
- C04B 2111/00439: {Physico-chemical properties of the materials not provided for elsewhere in C04B2111/00}
- C10G 2300/1025: Natural gas
- C10G 2300/1033: Oil well production fluids
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- Y02C 20/20: of methane
- Y02C 20/40: of CO2
- Y02E 50/30: Fuel from waste, e.g. synthetic alcohol or diesel
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- 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
- 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
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Finely divided ferrous carbonate absorbent, siderite granules or absorbent particles made by mixing, agglomerating and shaping finely powdered ferrous carbonate, preferably siderite, in combination with minor effective amounts of water or an optional binder, followed by drying, are used to treat and significantly reduce concentrations of hydrogen sulfide, carbonyl sulfide, organic disulfides, mercaptans and other sulfurous compounds and contaminants in gaseous and liquid fluid streams such as natural gas, light hydrocarbon streams, crude oil, acid gas mixtures, carbon dioxide gas and liquid streams, anaerobic gas, landfill gas, geothermal gases and liquids, and the like.

## Claims

### Claim 1

An absorbent for sulfur-containing compounds disposed in streams of gas, liquid, or mixed gas and liquid at temperatures ranging from about 52 to about 130° F. and at pressures ranging from about 200 to about 500 psig, the absorbent comprising ferrous carbonate as its principal absorptive component.

### Claim 2 (depends on 1)

The absorbent of claim 1, comprising from about 50 to about 100 weight percent ferrous carbonate.

### Claim 3 (depends on 2)

The absorbent of claim 2, comprising about 95 weight percent ferrous carbonate.

### Claim 4 (depends on 2)

The absorbent of claim 2, further comprising from about 2 to about 10 weight percent of a binder.

### Claim 5 (depends on 4)

The absorbent of claim 4, comprising about 5 weight percent of a binder.

### Claim 6 (depends on 1)

The absorbent of claim 1 wherein the ferrous carbonate is in the form of the mineral siderite.

### Claim 7 (depends on 6)

The absorbent of claim 6 wherein the siderite is in the form of granules.

### Claim 8 (depends on 6)

The absorbent of claim 6 wherein the siderite is in the form of agglomerates.

### Claim 9 (depends on 6)

The absorbent of claim 6 wherein the siderite is in the form of extrudates.

### Claim 10 (depends on 4)

The absorbent of claim 4 wherein the binder is calcium aluminate cement.

### Claim 11 (depends on 7)

The absorbent of claim 7 where the granules have particle sizes ranging between about 1/16 inch and about 5/16 inch.

### Claim 12 (depends on 9)

The absorbent of claim 9 wherein the extrudates have a length not exceeding about 5/16 inch.

### Claim 13 (depends on 1)

The absorbent of claim 1 in the form of agglomerated and densified powder.

### Claim 14 (depends on 1)

The absorbent of claim 1 in the form of particles selected from the group consisting of pellets, prills and spheroids.

### Claim 15 (depends on 13)

The absorbent of claim 13 comprising powdered siderite in combination with a binder.

### Claim 16 (depends on 15)

The absorbent of claim 15 wherein the binder comprises calcium aluminate.

### Claim 17 (depends on 15)

The absorbent of claim 15 comprising from about 50 to about 100 weight percent siderite, from about 2 to about 10 weight percent binder, and a moisture content less than 3 weight percent.

### Claim 18 (depends on 15)

The absorbent of claim 15 wherein the powdered siderite has a particle size of about 100 mesh.

### Claim 19 (depends on 13)

The absorbent of claim 13, made by blending powdered siderite and calcium aluminate cement in the presence of water, and thereafter extruding, sizing and drying the resultant product.

### Claim 20

A method for making an absorbent that is useful for removing sulfur-containing compounds disposed in streams of gas, liquid, or mixed gas and liquid by providing from about 50 to about 100 parts by weight of ferrous carbonate having a particle size of about 100 mesh, by blending with the ferrous carbonate from about 2 parts by weight to about 10 parts by weight cementitious binder and from about 15 to about 25 parts by weight water, by extruding the blended ferrous carbonate, cementitious binder and water to produce an extrudate of desired length, and by thereafter drying the extrudate to a moisture content less than 3 weight percent.

### Claim 21 (depends on 20)

The method of claim 20 wherein the ferrous carbonate is siderite.

### Claim 22 (depends on 20)

The method of claim 20 wherein the cementitious binder comprises calcium aluminate.

### Claim 23 (depends on 21)

The method of claim 21, wherein about 5 parts by weight cementitious binder and about 20 parts by weight water are blended with about 95 parts by weight siderite powder.

### Claim 24 (depends on 23)

The method of claim 23 wherein the siderite powder has a particle size of about 100 mesh.

### Claim 25

A method for absorbing sulfur-containing compounds disposed in a stream of gas, liquid, or mixed gas and liquid at temperatures ranging from about 52 to about 130° F. and at pressures ranging from about 200 to about 500 psig by providing an absorbent principally comprising ferrous carbonate as its principal absorptive component and by contacting the ferrous carbonate with the stream.

### Claim 26 (depends on 25)

The method of claim 25 wherein the ferrous carbonate is siderite.

### Claim 27 (depends on 26)

The method of claim 26 wherein the absorbent is in the form of pellets made from a blend of powdered siderite and a cementitious binder, together with sufficient water to hydrate the cement.

### Claim 28 (depends on 26)

The method of claim 26 wherein the pellets comprise from about 70 to about 100 weight percent siderite and from about 2 to about 10 weight percent cementitious binder.

### Claim 29 (depends on 27)

The method of claim 27 wherein the cementitious binder is calcium aluminate cement.

### Claim 30 (depends on 27)

The method of claim 27 wherein the pellets are extruded.

### Claim 31 (depends on 27)

The method of claim 27 wherein the pellets are dried to a moisture content less than 3 weight percent.

### Claim 32 (depends on 25)

The method of claim 25 wherein the sulfur-containing compounds are selected from the group consisting of hydrogen sulfide, carbonyl sulfide, organic disulfides and mercaptans.

### Claim 33 (depends on 27)

The method of claim 27 wherein the pellets are arranged in a bed.

### Claim 34 (depends on 33)

The method of claim 33 wherein the stream comprises a fluid selected from the group consisting of natural gas, natural gas liquids, light light hydrocarbons, crude oil, acid gas mixtures, gaseous carbon dioxide, anaerobic gas, landfill gas, and geothermal fluids.

### Claim 35 (depends on 25)

The method of claim 25 wherein the stream comprises sour gas inside a well bore and wherein the ferrous carbonate is finely divided and is distributed in a drilling mud that is circulated through the well bore.

### Claim 36 (depends on 1)

The absorbent of claim 1 wherein the sulfur-containing compounds are selected from the group consisting of hydrogen sulfide, carbonyl sulfide, organic disulfides and mercaptans.

### Claim 37 (depends on 1)

The absorbent of claim 1 wherein the stream comprises a fluid selected from the group consisting of natural gas, natural gas liquids, light hydrocarbons, crude oil, acid gas mixtures, gaseous carbon dioxide, anaerobic gas, landfill gas, and geothermal fluids.