Selective catalytic oxidation of ammonia to water and nitrogen

Information

  • Patent Grant
  • 7943547
  • Patent Number
    7,943,547
  • Date Filed
    Wednesday, September 14, 2005
    18 years ago
  • Date Issued
    Tuesday, May 17, 2011
    13 years ago
Abstract
A catalyst includes a platinum coating deposited on a silica support. The support has an average surface area between about 100 m2/g and about 120 m2/g. The platinum coating is between about 5 wt % and about l5 wt % of the catalyst. The combination of the selected surface area, silica support, and selected amount of platinum coating provides a catalytic activation temperature below 200° C. and avoids the formation of NOx.
Description
BACKGROUND OF THE INVENTION

This invention relates to catalysts, and more particularly, to platinum catalysts for oxidizing ammonia in vapor phase catalytic ammonia removal systems.


Catalytic systems are widely known and used for decomposing or oxidizing undesirable chemical species within a fluid. Catalytic systems are used in space vehicles and in space stations to remove ammonia and other chemicals from waste streams generated during a space mission. Typically, water-based waste streams are collected, distilled, and purified before being reused by a crew. The weight of such catalytic systems and the amount of energy that the catalytic systems use is minimized to reduce relatively high expenses related to space travel.


Conventional catalysts typically include an active metal deposited on a support material. Typically, the type of active metal and type of support material are selected based upon the application that the catalyst will be used in. Disadvantageously, currently available combinations of active metals and support materials for ammonia oxidation require temperatures above approximately 200° C. to oxidize ammonia and often result in the formation of nitrogen oxide (NOx). To minimize NOx formation, the catalyst is undesirably operated in a narrow temperature range above the catalysis activation temperature and below the NOx formation temperature.


Accordingly, there is a need for an ammonia catalyst that operates over a relatively large temperature range and at temperatures below 200° C. to avoid the formation of NOx.


SUMMARY OF THE INVENTION

A catalyst according to the present invention includes a platinum coating deposited on a silica support. A combination of the silica support material with a surface area between about 100 m2/g and about 120 m2/g, and between about 5 wt % and about 15 wt % of platinum provides complete selective catalytic oxidation of ammonia at temperatures as low as 150° C. and avoids the formation of NOx, until temperatures exceeding 200° C.


In one example, a reactor containing a catalyst is connected to a vaporizer. The vaporizer vaporizes liquid waste water containing ammonia. The catalyst oxidizes the gaseous ammonia to form nitrogen and water.





BRIEF DESCRIPTION OF THE DRAWINGS

The various features and advantages of this invention will become apparent to those skilled in the art from the following detailed description of the currently preferred embodiment. The drawings that accompany the detailed description can be briefly described as follows.



FIG. 1 is a schematic view of an example catalytic system according to the present invention.



FIG. 2 shows an example granule of a catalytic bed.



FIG. 3 shows a cross-section of the granule of FIG. 2.



FIG. 4 shows a cross-section of a second embodiment of the granule of FIG. 2.





DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT


FIG. 1 illustrates selected portions of an example catalytic system 10 for oxidizing ammonia and hydrocarbons, for example, from a vaporized feed stream. The catalytic system 10 includes a vaporizer 12 that receives a waste water that is collected, for example, from waste urine, wash water, and moisture condensate collected from operating systems on a space vehicle. The vaporizer 12, such as a boiler, vaporizes the waste water. A vaporized stream travels through a conduit 14 to a reactor 16. A heater 18 adjacent to the conduit 14 maintains an elevated temperature along a portion of the conduit 14 to minimize condensation of the vaporized stream.


The reactor 16 includes an ammonia catalyst 20 and a hydrocarbon catalyst 22. The ammonia catalyst 20 oxidizes the gaseous ammonia to produce gaseous nitrogen and gaseous water. The hydrocarbon catalyst 22 decomposes the gaseous hydrocarbons. A heater 23 near the ammonia catalyst 20 and hydrocarbon catalyst 22 maintains the ammonia catalyst 20 at a desired temperature.


The catalytic system 10 includes an oxygen source 24 connected to the conduit 14. A controller 26 in communication with the oxygen source 24 and the vaporizer 12 selectively opens or closes a valve 28 to supply gaseous oxygen into the conduit 14 to provide a selected amount of gaseous oxygen. This provides a benefit of achieving a desired ratio of gaseous oxygen to gaseous ammonia within the conduit 14. In one example, the ratio of gaseous oxygen to gaseous ammonia is set according to stoichiometry for oxidation of the gaseous ammonia at the ammonia catalyst 20 to produce gaseous nitrogen and gaseous water instead of NOx.


The catalytically converted species (e.g., nitrogen, water, and decomposed hydrocarbons) travel from the reactor 16 into a condenser 30. The condenser 30 is maintained at a relatively low temperature to condense the gaseous water. Liquid water is collected from the condenser 30 and fed out of a conduit 32 to a downstream use. Chemical species that were not condensed within the condenser 30 are fed through a conduit 34 and are collected in a receptacle 36 or vented to the environment.


A vacuum pump 38 connected downstream from the condenser 30 maintains a relatively low pressure in the catalytic system 10 to move the vapor stream through the reactor 16.



FIG. 2 shows a granule 48, or pellet, used in the ammonia catalyst 20 and FIG. 3 shows a cross-section of the granule 48. The granule 48 is made of a porous homogenous silica material having pores 50. As is known, relatively large numbers of granules 48 can be packed together to form a catalytic bed through which the vaporized stream flows.


The granule 48 includes an average surface area between about 100 m2/g and about 120 m2/g. In one example, the granule 48 is NorPro® silica provided by Saint-Gobain Ceramics & Plastics, Inc.


A platinum catalytic coating 54 is deposited on the granule 48 within the pores 50 and on the outer surface 55 of the granule 48. In one example, the platinum catalytic coating 54 is applied using a known incipient wetness process. In another example, the platinum catalytic coating 54 is applied using a vapor deposition process. The platinum comprises between about 5 wt % and about 15 wt % of the granule 48. In one example, the amount is approximately 10 wt %.


In an incipient wetness process, a platinum salt, such as platinum chloride, is impregnated into the granule 48. The salt fills the volume within the pores 50. The composite of the granule 48 and the platinum salt solution is then dried in air, for example, to remove at least a portion of a liquid carrier of the platinum salt solution. During the drying, platinum chloride is converted to a platinum oxide on the surfaces of the granule 48. The platinum oxide is then reduced to platinum metal in a known manner using hydrogen gas to form the platinum catalytic coating 54. At this stage, some residual chloride from the platinum salt may remain in the platinum catalytic coating 54. The granule 48 is then washed with water to remove at least a portion of the residual chloride and dried to remove the wash water.


The amount of platinum deposited can be controlled by controlling the concentration of the platinum salt in the solution. As is known, the volume of the pores 50 can be determined empirically. The pore 50 volume in combination with a selected concentration of platinum salt in the solution results in a determinable amount of platinum metal deposited on the surfaces of the granule 48 (including the pore 50 surfaces).


The combination of the selected surface area, homogenous silica granule 48, and selected amount of platinum results in selective oxidation of ammonia at temperatures under 200° C. This provides the benefit of operating the ammonia catalyst 20 within a temperature window of, for example, 150° C. to 200° C. to form nitrogen and water instead of NOx.


Alternatively, as shown in FIG. 4, the granule 48 is made of relatively low surface area silica, alumina, metal, or other material and a relatively high surface area silica washcoat 52 is deposited in a known manner within the pores 50 and on the outer surface 55 of the granule 48. The silica washcoat 52 increases the surface area of the low surface area material. The platinum catalytic coating 54 is deposited on the silica washcoat as described above.


In another example, the granule 48 includes a silica aerogel for supporting the platinum. The silica aerogel can be used in granule shape or in other shapes such as disks. The silica aerogel includes an average surface area of about 800 m2/g. The relatively high surface area results in a weak support that may crumble easily, however, a silica aerogel may be suitable for application where strength is not a significant concern.


In one example, the silica aerogel includes about 16 wt % platinum deposited on the surfaces using an incipient wetness process as described above. The combination of the silica aerogel and 16 wt % platinum provides the benefit of an ammonia catalytic activation temperature that is about 125° C. and avoids formation of NOx.


Although a preferred embodiment of this inventiori has been disclosed, a worker of ordinary skill in this art would recognize that certain modifications would come within the scope of this invention. For that reason, the following claims should be studied to determine the true scope and content of this invention.

Claims
  • 1. A catalyst comprising: a silica support including an average surface area between about 100 m2/g and about 120 m2/g; anda catalyst coating including platinum, said catalyst coating being supported by said support, and said catalyst coating comprising between about 5% and about 15% of a combined mass of said support and said catalyst coating.
  • 2. The catalyst as recited in claim 1, wherein said silica support includes a porous silica pellet.
  • 3. The catalyst as recited in claim 1, wherein said catalyst coating consists essentially of platinum.
  • 4. The catalyst as recited in claim 1, wherein said catalyst coating comprises about 10% of the combined mass.
  • 5. A catalyst comprising: a silica support including an average surface area between about 100 m2/g and about 120 m2/g, said silica support further comprises a silica washcoat and a catalyst coating deposited on said silica washcoat; andsaid catalyst coating including' platinum, said catalyst coating being supported by said support, and said catalyst coating comprising between about 5% and about 15% of a combined mass of said support and said catalyst coating.
  • 6. A catalyst comprising: a silica support; anda catalyst coating including platinum, said catalyst coating being supported by said support, and said catalyst coating comprising between about 5% and about 15% of a combined mass of said support and said catalyst coating, wherein said catalyst coating has an ammonia catalyst activation temperature below about 200° C.
  • 7. A catalyst comprising: a support including a silica aerogel having an average surface area of about 800 m2/g;a platinum catalyst coating on said support, said platinum catalyst coating having an ammonia catalyst activation temperature below about 200° C.
  • 8. The catalyst as recited in claim 7, wherein said platinum catalyst coating comprises about 16% platinum by mass.
  • 9. The catalyst as recited in claim 7, wherein said ammonia catalyst activation temperature is about 125° C.
  • 10. A silica support including an average surface area between about 100 m2/g and about 120 m2/g and including a porous silica pellet including a porous inner silica core, said porous silica pellet being coated on exterior surfaces thereof with a catalyst coating; and the catalyst coating including platinum, said catalyst coating being supported by said support, and said catalyst coating comprising between about 5% and about 15% of a combined mass of said support and said catalyst coating.
  • 11. The silica support as recited in claim 10, wherein the porous inner silica core includes pores having pore surfaces coated with the catalytic coating.
  • 12. A catalyst comprising: a support including a silica aerogel having an average surface area of about 800 m2/g, wherein said support is a porous silica pellet including a porous inner silica core coated on exterior surfaces thereof with a platinum catalyst coating; andsaid platinum catalyst coating being on said support, said platinum catalyst coating having an ammonia catalyst activation temperature below about 200° C.
US Referenced Citations (45)
Number Name Date Kind
2079404 Harris May 1937 A
2083824 Bond et al. Jun 1937 A
2123732 Walsh et al. Jul 1938 A
2200522 Streicher May 1940 A
2623860 Haensel Dec 1952 A
2854401 Weisz Sep 1958 A
2854403 Weisz Sep 1958 A
2861958 Barrett Nov 1958 A
2891013 Myers Jun 1959 A
2961414 Lefrancois et al. Nov 1960 A
3161605 Stiles et al. Dec 1964 A
3522269 Fritze et al. Jul 1970 A
3894965 Foster et al. Jul 1975 A
3903020 Sergeys et al. Sep 1975 A
3956185 Yagi et al. May 1976 A
4076792 Foster et al. Feb 1978 A
4077913 Acres et al. Mar 1978 A
4157316 Thompson et al. Jun 1979 A
4537873 Kato et al. Aug 1985 A
4757045 Turner et al. Jul 1988 A
4791091 Bricker et al. Dec 1988 A
4904633 Ohata et al. Feb 1990 A
4956326 Yoneda et al. Sep 1990 A
5061464 Cordonna et al. Oct 1991 A
5128114 Schwartz Jul 1992 A
5145826 Hirschberg et al. Sep 1992 A
5175136 Felthouse Dec 1992 A
5202299 Symons et al. Apr 1993 A
5208200 Soled et al. May 1993 A
5275995 Bellussi et al. Jan 1994 A
5352645 Schwartz Oct 1994 A
5491120 Voss et al. Feb 1996 A
5518978 Flego et al. May 1996 A
5571763 Takemoto et al. Nov 1996 A
5879539 Mignard et al. Mar 1999 A
6022826 Deeba et al. Feb 2000 A
6165430 Kudla et al. Dec 2000 A
6255249 Voss et al. Jul 2001 B1
7030055 Yaluris et al. Apr 2006 B2
7452844 Hu et al. Nov 2008 B2
7563743 Euzen et al. Jul 2009 B2
7563744 Klein et al. Jul 2009 B2
7659224 Shimazaki et al. Feb 2010 B2
20010036433 Euzen et al. Nov 2001 A1
20060183636 Klein et al. Aug 2006 A1
Related Publications (1)
Number Date Country
20070059228 A1 Mar 2007 US