Zinc oxide based sorbent and process for preparing same

Patent metadata

Field	Value
Publication number	US-11491457-B2
Application number	US-201816635790-A
Country	US
Kind code	B2
Filing date	Aug 1, 2018
Priority date	Aug 1, 2017
Publication date	Nov 8, 2022
Grant date	Nov 8, 2022

Abstract

Zinc oxide-based sorbents, and processes for preparing and using them are provided, wherein the sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents contain an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two-phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl2O4) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 50 nm (500 Angstroms). Preferably the sorbents are prepared by using an alkali metal base to convert a precursor mixture, containing a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component, with the resulting sorbent having a sodium level within a desired range.

First claim

What is claimed is:

1. A fluidizable, attrition-resistant sorbent for removing at least one reduced sulfur species from a feed stream comprising:
substantially spherical particles, said particles comprising at least 75 wt % of an active zinc component consisting essentially of a zinc oxide phase and a zinc aluminate phase, each of said phases having a crystallite size of less than about 50 nm as determined by x-ray diffraction line broadening analysis,
said active zinc component having a total zinc oxide content, calculated based on the combined zinc oxide of said zinc oxide phase and said zinc aluminate phase, of from about 50 wt %, to about 80 wt %, based on the weight of said active zinc component, wherein the residual sodium level in the solid phase is in the range of between 25 parts per million by weight of sodium and 2500 parts per million by weight of sodium.

2. The fluidizable, attrition-resistant sorbent of claim 1 , wherein the residual sodium level in the solid phase is in the range of between 50 parts per million by weight of sodium and 1000 parts per million by weight of sodium.

3. The fluidizable, attrition-resistant sorbent of claim 1 , wherein the residual sodium level in the solid phase is in the range of between 75 parts per million by weight of sodium and 750 parts per million by weight of sodium.

4. The fluidizable, attrition-resistant sorbent of claim 1 , wherein the reduced sulfur species is H 2 S or COS.

5. A process for preparing a fluidizable, attrition resistant, active zinc oxide containing sorbent comprising the steps:
forming a first slurry by combining an aqueous solution of a zinc oxide precursor and aluminum oxide precursor with an aqueous solution of an alkali metal hydroxide such that the solids content comprises a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, said precipitated zinc oxide precursor and said precipitated aluminum oxide precursor being present in an amount, calculated as ZnO, and Al 2 O 3 , respectively, such that said precipitated zinc oxide precursor constitutes between about 50 wt %, and about 80 wt %, of the total solids content of said precipitated zinc oxide precursor and said precipitated aluminum oxide precursor in said slurry, and such that the pH of this slurry during the mixing and combining step is maintained between the values of 5.5 and 7.5;
separating the liquid phase of the first slurry from the solid phase by a separating means; washing the filtered solid phase with water, preferably deionized water, to achieve a residual sodium level in the solid phase of between 25 parts per million by weight of sodium and 2500 parts per million by weight of sodium;
treating the separated solid material from the first slurry with water and concentrated acid to generate a second slurry wherein the pH of the second slurry is adjusted with acid to be between 3.5 and 5.0;
spray drying the second slurry to form spray dried particles; and
calcining said spray dried particles to provide fluidizable, attrition resistant, active zinc oxide containing sorbent particles comprising a two-phase component consisting essentially of a zinc oxide phase and a zinc aluminate phase.

6. The process of claim 5 , wherein said spray drying step is conducted under conditions sufficient to provide calcined particles having a size range of between 35 μm and 175 μm.

7. The process of claim 5 , wherein said zinc oxide constitutes at least about 50 wt % of the total solids content of said zinc oxide precursor and said aluminum oxide precursor in said slurry.

8. The process of claim 5 , wherein the active zinc oxide containing sorbent particles comprise zinc oxide trains less than 50 nm diameter.

9. The process of claim 5 , wherein the active zinc oxide containing sorbent particles comprise zinc oxide grains about 13 nm to about 20 nm diameter.

10. The process of claim 5 , wherein said slurry additionally comprises at least one additional material selected from the group consisting of promoter precursors, binder precursors and refractory oxide precursors, and wherein said additional material is present in amount selected to provide fluidizable, attrition resistant, active zinc oxide containing sorbent particles containing at least about 75 wt % of said two-phase component consisting essentially of a zinc oxide phase and a zinc aluminate phase.

11. The process of claim 5 , wherein all or part of the alkali metal hydroxide is replaced with an alkali metal carbonate.

12. The process of claim 5 , wherein the alkali metal hydroxide is sodium hydroxide.

13. The process of claim 5 , wherein the residual sodium level in the solid phase is between 50 parts per million by weight of sodium and 1000 parts per million by weight of sodium.

14. The process of claim 5 , wherein the acid used for acidification of the second slurry is nitric acid.

15. The process of claim 5 , wherein the pH range of the second slurry is adjusted to be between 4.0 and 4.5.

16. The process of claim 5 , wherein the formation of the first slurry is performed at a temperature of ambient to about 85° C.

17. The process of claim 16 , wherein the formation of the first slurry is performed at a temperature of about 50° C. to about 80° C.

18. The process of claim 17 , wherein the formation of the first slurry is performed at a temperature of about 65° C. to about 75° C.

19. The process of claim 5 , wherein the separating of the liquid phase of the first slurry from the solid phase includes a washing process performed at temperatures between ambient and about 85° C.

20. The process of claim 5 , wherein the separating of the liquid phase of the first slurry from the solid phase includes a washing process performed at temperatures between about 50° C. and about 80° C.

21. The process of claim 5 , wherein said spray dried particles are calcined at about 500° C. to about 900° C.

Assignees

• Res Triangle Inst

Inventors

• Shen Jian-Ping
• Norman Jason S
• Turk Brian S
• Gupta Raghubir

Classifications

• B01D2253/1124

  Metal oxides · CPC title

• B01J20/28011

  Other properties, e.g. density, crush strength · CPC title

• B01D2253/30

  Physical properties of adsorbents · CPC title

• B01J20/08 Primary

  comprising aluminium oxide or hydroxide; comprising bauxite · CPC title

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title