Adsorptive desulfurization

Patent metadata

Field	Value
Publication number	US-2016175806-A1
Application number	US-201514972339-A
Country	US
Kind code	A1
Filing date	Dec 17, 2015
Priority date	Dec 17, 2014
Publication date	Jun 23, 2016
Grant date	—

Abstract

The disclosure relates to a method for removing sulfur-containing compounds from a fluid. The method involves adding manganese oxide to the fluid; doping the manganese oxide in situ with iron, cobalt, or combinations thereof to give a doped manganese oxide adsorbent; and contacting the fluid with a selected amount of the doped manganese oxide adsorbent and at a selected temperature and pressure sufficient for the doped manganese oxide adsorbent to preferentially adsorb the sulfur-containing compounds in the fluid. The disclosure also relates to a process for preparing a doped manganese oxide adsorbent, and a doped manganese oxide adsorbent prepared by the process. The disclosure further relates to a method for tuning structural properties (e.g., surface area, pore size and pore volume) of a doped manganese oxide adsorbent.

First claim

What is claimed is:

1 . A method for removing sulfur-containing compounds from a fluid, the method comprising:
adding manganese oxide to the fluid; doping the manganese oxide in situ with iron, cobalt, or combinations thereof to give a doped manganese oxide adsorbent; and contacting the fluid with a selected amount of the doped manganese oxide adsorbent and at a selected temperature and pressure sufficient for the doped manganese oxide adsorbent to preferentially adsorb the sulfur-containing compounds in the fluid.

2 . The method of claim 1 , wherein the contacting is conducted at a temperature of 300° C. or less.

3 . The method of claim 1 , wherein the manganese oxide is a manganese oxide octahedral molecular sieve (OMS) material.

4 . The method of claim 1 , wherein the iron doped manganese oxide adsorbent has a Birnessite type structure or a Cryptomelane type structure.

5 . The method of claim 1 , wherein the sulfur-containing compounds comprises hydrogen sulfide, thiols (mercaptans), and/or derivatives thereof.

6 . The method of claim 1 , wherein iron in the iron doped manganese oxide adsorbent is present in an amount of from about 0.1 weight percent to about 25 weight percent, and wherein cobalt in the cobalt doped manganese oxide adsorbent is present in an amount of from about 0.1 weight percent to about 25 weight percent.

7 . The method of claim 1 , wherein the doped manganese oxide adsorbent includes a binder material.

8 . The method of claim 1 , further comprising regenerating the doped manganese oxide adsorbent by anion exchange at a temperature and for a period to time sufficient to substantially remove the sulfur-containing compounds.

9 . The method of claim 1 , wherein the doped manganese oxide adsorbent is adapted to adsorb sulfur-containing compounds comprising thiols, sulfides, thiophenes and alkyl derivatives thereof.

10 . The method of claim 1 , wherein the doped manganese oxide adsorbent has a sulfur sorption capacity of from about 30 to about 60 g-S/100 g sorbent after sulfidation at 300° C., and wherein the doped manganese oxide+binder adsorbent has a sulfur sorption capacity of from about 30 to about 60 g-S/100 g sorbent after sulfidation at 300° C.

11 . The method of claim 1 , further comprising conducting the process under reaction conditions sufficient to tune the structural properties of the doped manganese oxide adsorbent.

12 . The method of claim 11 , wherein the structural properties comprise surface area, pore size and pore volume.

13 . A process for preparing an adsorbent material, the process comprising:
adding manganese oxide to the fluid; doping the manganese oxide in situ with iron, cobalt, or combinations thereof to give a doped manganese oxide adsorbent; and contacting the fluid with a selected amount of the doped manganese oxide adsorbent and at a selected temperature and pressure and for a period of time sufficient to prepare a doped manganese oxide adsorbent material.

14 . The process of claim 13 , wherein the contacting is conducted at a temperature of 300° C. or less.

15 . The process of claim 13 , wherein the manganese oxide is a manganese oxide octahedral molecular sieve (OMS) material.

16 . The process of claim 13 , wherein the iron doped manganese oxide adsorbent has a Birnessite type structure or a Cryptomelane type structure.

17 . The process of claim 13 , wherein iron in the iron doped manganese oxide adsorbent is present in an amount of from about 0.1 weight percent to about 25 weight percent, and wherein cobalt in the cobalt doped manganese oxide adsorbent is present in an amount of from about 0.1 weight percent to about 25 weight percent.

18 . The process of claim 13 , wherein the doped manganese oxide adsorbent includes a binder material.

19 . The process of claim 13 , wherein the doped manganese oxide adsorbent is adapted to adsorb sulfur-containing compounds comprising thiols, sulfides, thiophenes and alkyl derivatives thereof.

20 . The process of claim 13 , wherein the doped manganese oxide adsorbent has a sulfur sorption capacity of from about 30 to about 60 g-S/100 g sorbent after sulfidation at 300° C., and wherein the doped manganese oxide+binder adsorbent has a sulfur sorption capacity of from about 30 to about 60 g-S/100 g sorbent after sulfidation at 300° C.

21 . The process of claim 13 , further comprising conducting the process under reaction conditions sufficient to tune the structural properties of the doped manganese oxide adsorbent.

22 . The process of claim 21 , wherein the structural properties comprise surface area, pore size and pore volume.

23 . An adsorbent material prepared by a process, the process comprising:
adding manganese oxide to the fluid; doping the manganese oxide in situ with iron, cobalt, or combinations thereof to give a doped manganese oxide adsorbent; and contacting the fluid with a selected amount of the doped manganese oxide adsorbent and at a selected temperature and pressure and for a period of time sufficient to prepare a doped manganese oxide adsorbent material.

24 . A composition comprising at least one derivative, doped or reduced compound of the formula
MMn 8 O 16
wherein M is an alkali metal or an alkaline earth metal.

25 . The composition of claim 24 , comprising at least one derivative, doped or reduced compound of the formula
KMn 8 O 16

26 . The composition of claim 24 , comprising at least one derivative, doped or reduced compound of the formula
M v Co x Fe y Mn z O 16
wherein M is an alkali metal or an alkaline earth metal, and v , x , y , and z independently have a value from 0 to 8.

27 . The composition of claim 24 , which has a Birnessite type structure or a Cryptomelane type structure.

Assignees

• Univ Connecticut

Inventors

• Suib Steven L
• Pahalagedara Lakshitha R
• Kuo Chung-Hao

Classifications

• C01P2004/04

  obtained by TEM, STEM, STM or AFM · CPC title

• C01P2002/70

  defined by measured X-ray, neutron or electron diffraction data · CPC title

• C01P2002/52

  containing elements as dopants · CPC title

• C01P2002/50

  Solid solutions · CPC title

• C01G45/1221

  Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof · CPC title