Agglomeration-resistant desulfurizing product

• US 9,713,786 B2
• Filed: 12/29/2011
• Issued: 07/25/2017
• Est. Priority Date: 01/04/2011
• Status: Active Grant

• Current Assignee: M-I LLC (Schlumberger NV)
• Original Assignee: M-I LLC (Schlumberger NV)
• Inventors: Braga, Thomas G.
• Primary Examiner(s): Dunn, Colleen
• Assistant Examiner(s): Soliman, Haytham
• Application Number:
  US13/976,389
• Publication Number:
  US 20130272943A1
• Time in Patent Office: 2,035 Days
• Field of Search: 208 15, 208208, 208244, 208 16, 502402
• CPC Class Codes: B01D 53/00 Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols, recovery of volatile solvents by condensation B01D5/00; sublimation B01D7/00; cold traps, cold baffles B01D8/00; working-up undefined gaseous mixtures obtained by cracking hydrocarbon oils C10G70/00; cleaning coal gas C10K; working-up of natural gas, or synthetic natural gas, C10L3/10; separation of difficult-to-condense gases or air by liquefaction F25J; for investigating materials G01N30/00
• CPC Class Codes: B32B 15/046 of foam
• CPC Class Codes: B32B 15/10 of wood
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/703 Activation
• CPC Class Codes: C10G 70/00 Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
• CPC Class Codes: C10L 3/103 Sulfur containing contaminants
• CPC Class Codes: Y10T 428/31989 Of wood

Abstract

Disclosed herein is an agglomeration-resistant desulfurizing product for removing contaminants from a fluid stream. The agglomeration-resistant desulfurizing product comprising a metal oxide composition for reacting with contaminants and a polymeric crystallization inhibitor for reducing the agglomeration of the desulfurizing product resulting from using the desulfurizing product. A method to produce the agglomeration-resistant desulfurizing product and a method to treat a fluid stream is also disclosed.

Claims

1. An agglomeration-resistant desulfurizing product for removing contaminants from a fluid stream, the desulfurizing product comprising:

a solid product, comprising;

(a) a metal oxide composition that comprises a primary component, wherein the primary component comprises at least one metal oxide of the formula Me_xO_y—

(H₂O)_z, wherein Me is selected from groups 4-12 of the periodic table of elements, O is oxygen;

1≦

x≦

3;

1≦

y≦

4, and 0≦

z≦

10; and

(b) a polymeric crystallization inhibitor;

wherein the agglomeration-resistant desulfurizing product does not contain a silicate binder compound.

2. The agglomeration-resistant desulfurizing product of claim 1, wherein the polymeric crystallization inhibitor is at an amount that is in the range of about 1000 ppm by weight to about 10 wt % based on the weight of the metal oxide composition.

3. The agglomeration-resistant desulfurizing product of claim 2, wherein the polymeric inhibitor comprises:

a salt of acrylamido-methyl propane sulfonate/acrylic acid copolymer (AMPS/AA);

a phosphonated maleic copolymer (PHOS/MA);

a salt of polymaleic acid/acrylic acid/acrylamido-methyl propane sulfonate terpolymers (PMA AMPS); and

/or

a copolymer that comprises an acrylamide moiety, a quaternary ammonium moiety, a quaternary ammonium salt moiety, an acrylate moiety, an acrylic acid moiety, or combination thereof.

4. The agglomeration-resistant desulfurizing product of claim 1, wherein the polymeric crystallization inhibitor comprises an acrylamide moiety, a quaternary ammonium moiety, a quaternary ammonium salt moiety, an acrylate moiety, an acrylic acid moiety, or combination thereof.

5. The agglomeration-resistant desulfurizing product of claim 4, wherein the acrylamide moiety is selected from the group consisting of acrylamide, (meth)acrylamide, diacetone acrylamide, N-methylolacrylamide, and combinations thereof.

6. The agglomeration-resistant desulfurizing product of claim 4, wherein the quaternary ammonium salt is obtained by cationizing a tertiary-amino-containing monomer and a cationizing agent, wherein the tertiary-amino-containing monomer is selected from the group consisting of N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene and p-diethylaminoethylstyrene, and wherein the cationizing agent is selected from the group consisting of a halogenated alkyl, a dialkylsulfuric acid, an epichlorohydrin-added tertiary amine mineral acid salt, an inorganic salt, and a carboxylic acid.

7. The agglomeration-resistant desulfurizing product of claim 4, wherein the quaternary ammonium salt is selected from the group consisting of dialkyldiallylammonium salts, polyvinyl benzyl trialkyi ammonium salts, salts of polyepichlorohydrin quaternized with trialkyi amine, polymethacrylarnidoalkyltrialkyl ammonium salts, polymethacryloyloxyalkyltrialkyl ammonium salts, and polymethacryloyloxyalkyl diallyl hydroxyalkyl ammonium salt, wherein the alkyl is preferably a C₁-C₃ alkyl group.

8. The agglomeration-resistant desulfurizing product of claim 7, wherein the quaternary ammonium salt is selected from the group consisting of polyvinyl benzyl trimethyl ammonium salts, salts of polyepichlorohydrin quaternized with trimethyl amine, polymethacrylamidopropyltrimethyl ammonium salts, polymethaoryloyloxyethyltrimethyl ammonium salts, and polymethacryloyloxyethyl dimethyl hydroxyethyl ammonium salt.

9. The agglomeration-resistant desulfurizing product of claim 4, wherein the quaternary ammonium salt is selected from the group consisting of dimethyldiallylammonium salts, acrylamide derivatives of a dimethyldiallylammonium salts, and acrylic acid derivatives of dimethyldiallylammonium salts.

10. The agglomeration-resistant desulfurizing product of claim 9, wherein the quaternary ammonium salt is selected from the group consisting of dimethyldiallylammonium chloride, acrylamidoethyltrimethylammonium chloride, acrylamide/dimethylaminoethyl acrylate methyl chloride quaternary ammonium salt, poly(acrylamide/dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt), poly(acrylamide/diallyldimethyl ammonium chloride), poly(dimethylaminoethyl acrylate methyl chloride quaternary ammonium salt), and poly(dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt).

11. The agglomeration-resistant desulfurizing product of claim 4, wherein the polymeric crystallization inhibitor is an acrylamide moiety-quaternary ammonium salt moiety copolymer.

12. The agglomeration-resistant desulfurizing product of claim 11, wherein the copolymer has a molar ratio of acrylamide moiety to quaternary ammonium salt moiety that is in the range of about 1:

5 to about 5;

1.

13. The agglomeration-resistant desulfurizing product of claim 12, wherein the quaternary ammonium sail moiety is a diallyldimethylammonium salt and the copolymer has a molar ratio of acrylamide moiety to diallyldimethylammonium salt that is in the range of about 1:

2 to about 2;

1.

14. The agglomeration-resistant desulfurizing product of claim 13, wherein the polymeric crystallization inhibitor is a poly(acrylamide-co-diallyldimethylammonium chloride).

15. The agglomeration-resistant desulfurizing product of claim 4, wherein the polymeric crystallization inhibitor is an acrylic acid moiety-acrylamide moiety-quaternary ammonium salt moiety copolymer.

16. The agglomeration-resistant desulfurizing product of claim 15, wherein the copolymer has molar ratio of the acrylic acid moiety to the acrylamide moiety that is in the range of about 2:

1 to about 1;

3, and the copolymer has a molar ratio of the acrylamide moiety to the quaternary ammonium salt moiety that is in the range of about 1;

5 to about 5;

1.

17. The agglomeration-resistant desulfurizing product of claim 1, wherein the Me is Fe, Zn, or combinations thereof.

18. The agglomeration-resistant desulfurizing product of claim 1, wherein the primary component is selected from the group consisting of comprises Fe_aO_b, hydrated forms of Fe_aOb, ZnO, hydrated forms of ZnO, and combinations thereof, wherein 1≦

a≦

3 and 1≦

b≦

4.

19. The agglomeration-resistant desulfurizing product of claim 1, wherein the primary component is selected from the group consisting of FeO, Fe₂O₃, Fe₃O₄, Fe(OH)₂, Fe(OH)₃, Fe(OH)₂, FeOOH, Fe₅HO₈, hydrates thereof, and a combinations thereof.

20. The agglomeration-resistant desulfurizing product of claim 1, wherein the primary component is selected from the group consisting of Fe₂O₃, Fe₃O₄, hydrates thereof, and combinations thereof.

21. The agglomeration-resistant desulfurizing product of claim 1, wherein the metal oxide composition further comprises an activator component that comprises one or metal oxides that are different from that of the primary component and selected from the group consisting of Cu₂O, CuO, Ag₂O, Au₂O₃, PtO₂, CdO, NiO₂, Ni₂O₃, PdO, PbO, Pb₃O₄, PbO₂, Pb₂O₃, Pb₁₂O₁₉, HgO, SnO, Sn₂, CoO, Co₂O₃, Co₃O₄, MnO, Mn₃O₄, Mn₂O₃, MnO₂, Mn₂O₇, Al₂O₃, and combinations thereof.

22. The agglomeration-resistant desulfurizing product of claim 21, wherein the activator component is at an amount that is in the range of about 0.5 wt % to about 5 wt % of the primary component.

23. The agglomeration-resistant desulfurizing product of claim 22, wherein the activator component is selected from the group consisting of Cu₂O, CoO, and combinations thereof.

24. The agglomeration-resistant desulfurizing product of claim 1, wherein agglomeration resistant product is a supported-type product that further comprises a carrier.

25. The agglomeration-resistant desulfurizing product of claim 24, wherein primary component is at an amount that is in the range of about 20 wt % to about 45 wt % of the desulfurizing product and the carrier is selected from the group consisting of wood chips and porous mineral carriers.

26. The agglomeration-resistant desulfurizing product of claim 1, wherein agglomeration resistant product is a compressed-type product that further comprises a binder.

27. The agglomeration-resistant desulfurizing product of claim 26 wherein primary component is at an amount that is greater than or equal to about 80 wt % of the desulfurizing product and the binder is at an amount that is at an amount that is in the range of about 1 wt % to about 10 wt % of the desulfurizing product.

28. The agglomeration-resistant desulfurizing product of claim 16, wherein the copolymer has a molar ratio of the acrylic acid moiety to the quaternary ammonium salt moiety to the acrylamide moiety that is in the range of about 1:

2;

1 to about 1;

1;

1.

29. The agglomeration-resistant desulfurizing product of claim 1, wherein the polymeric crystallization inhibitor is a copolymer.

30. The agglomeration-resistant desulfurizing product of claim 1, wherein the solid product has a homogeneous mixture of the metal oxide and the polymeric crystallization inhibitor.

31. The agglomeration-resistant desulfurizing product of claim 1, wherein the polymeric crystallization inhibitor is on the surface of the metal oxide.