Catalyst and process for oxidation and removal of nitrogen oxides (NOx) from combustion gases
View Patent ↗A bi-functional oxidation catalyst and process for catalytic oxidation and removal of nitrogen oxides (NO x ) from combustion gases derived from combustion of carbonaceous fuels such as coal, oil, or natural gas. The bi-functional catalyst includes adsorption and oxidation function metal oxides provided in adjacent close intimate contact by utilizing a binding agent, such as carboxylic acid and calcining to provide a metal oxide complex having a crystalline form. Such nitrogen oxides (NO x ) contained in the combustion gases are initially catalytically oxidized to at least about 50 vol % NO 2 and some higher oxides by contact with the bi-functional catalyst at 170-550° F. temperature. The combustion gas containing the partially oxidized NO x is then preferably further chemically oxidized by being mixed with a chemical oxidant such as ozone (O 3 ) in a molar ratio of the chemical oxidant 3 to NO x in the range of 0.5:1-1.2:1 to produce higher oxides of nitrogen such as substantially N 2 O 5 . The further treated combustion gas containing the N 2 O 5 is next scrubbed with a suitable scrubbing liquid such as water to effectively remove the nitrogen oxides (NO x ) and produce a clean treated flue gas stream containing less than about 15 ppm nitrogen oxides and suitable for environmentally safe discharge to the atmosphere.
1. A bi-functional catalyst useful for oxidation and removal of nitrogen oxides (NOx) contained in fuel combustion gases, the catalyst comprising:
an adsorption function metal oxide component comprising at least one metal oxide selected from the group consisting of oxides of barium, cesium, lanthanum, strontium, and zirconium,
wherein said adsorption metal oxide component includes lanthanum,
said adsorption function metal oxide component providing adsorption function and adsorption sites for nitrogen oxides in fuel combustion gases; and
an oxidation function metal oxide component comprising at least one metal oxide selected from the group consisting of chromium, cobalt, copper, iron, manganese, and platinum,
wherein said oxidation metal oxide component includes at least one of copper or manganese promoted with platinum,
said oxidation function metal oxide component providing an oxidation function and oxidation sites for nitrogen oxides in fuel combustion gases,
said adsorption metal oxide component and said oxidation metal oxide component being combined together in close intimate contact so that said adsorption metal oxide component and said oxidation metal oxide component are chemically bonded closely together so as to form a metal oxide complex having a crystalline structure,
said adsorption sites and oxidation sites for nitrogen oxides within the bi-functional catalyst being adjacent to each other and arranged so as to promote adsorption and oxidation of nitrogen oxides when exposed to fuel combustion gases containing nitrogen oxides,
the molar ratio of metal within the adsorption function metal oxide component to metal within the oxidation function metal oxide component being in a ratio range of 0.1:1 to 5:1 in the bi-functional catalyst.
2. The bi-functional catalyst of claim 1 , wherein said oxidation function metal oxide component includes copper, manganese, and platinum, and the molar ratio of metal within the adsorption function metal oxide component to metal within the oxidation function metal oxide component is in range of about 0.2:1 to 2:1.
3. The bi-functional catalyst of claim 1 , wherein said adsorption function metal oxide component includes barium (Ba), and said metal oxide oxidation component includes copper (Cu) and manganese (Mn) promoted with platinum (Pt).
4. The bi-functional catalyst of claim 1 , wherein said adsorption metal oxide component includes barium (Ba), and said oxidation metal oxide component includes copper (Cu), and optionally manganese (Mn), promoted with platinum (Pt).
5. The bi-functional catalyst of claim 1 , wherein said bi-functional catalyst is provided on a porous support material having surface area of at least about 50 m 2 /g.
6. A bi-functional catalyst useful for oxidation and removal of nitrogen oxides (NOx) contained in fuel combustion gases, the catalyst comprising:
an adsorption function metal oxide component comprising lanthanum and providing adsorption function and adsorption sites nitrogen oxides in fuel combustion gases; and
an oxidation function metal oxide component comprising at least one of copper or manganese promoted with platinum and providing oxidation function and oxidation sites for nitrogen oxides in fuel combustion gases,
said adsorption metal oxide component and said oxidation metal oxide component being combined intimately together so that said adsorption metal oxide component and said oxidation metal oxide component are chemically bonded closely together so as to form a metal oxide complex having a crystalline structure,
said adsorption sites and oxidation sites for nitrogen oxides within the bi-functional catalyst being adjacent to each other and arranged so as to promote adsorption and oxidation of nitrogen oxides when exposed to fuel combustion gases containing nitrogen oxides,
the molar ratio of metal within the adsorption function metal oxide component to metal within the oxidation function metal oxide components being in a range of 1.2:1 to 2:1,
said metal oxide components being provided on a porous inert support material having surface area of 50-500 m 2 /g.
7. A method for making a bi-functional catalyst suitable for catalytic oxidation of nitrogen oxides (NOx) contained in fuel combustion gases, comprising:
(a) providing an aqueous solution of adsorption function metal ions selected from the group consisting of barium, cesium, lanthanum, strontium, and zirconium and combinations thereof for providing an adsorption function and adsorption sites in the bi-functional catalyst for adsorbing nitrogen oxide contained in combustion gases;
(b) providing an aqueous solution of oxidation function metal ions selected from the metals group consisting of chromium, cobalt, copper, iron, manganese and platinum for providing an oxidation function and oxidation sites for in the bi-functional catalyst oxidizing nitrogen oxides in combustion gases,
said adsorption function metal ions having a molar ratio to the oxidation function metal ions in the range of 0.1:1 to 5:1;
(c) mixing said absorption and oxidation function metal ion solutions together and adding a binding agent acid having at least two functional groups selected for providing close intimate contact of said metal ions to form a precursor solution;
(d) drying said precursor solution and heating to a temperature of 500-800° C. (930-1470° F.) to form a metal oxide complex precursor material, then cooling the metal oxide complex precursor material; and
(e) forming a second solution of oxidation function metal ions and a platinum salt, and impregnating said precursor material with said second solution, then drying and calcining the impregnated material at 500-800° C. temperature and cooling to yield the bi-functional catalyst.
8. The method for making a bi-functional catalyst of claim 7 , wherein the binding agent acid comprises carboxylic acid having a molar ratio of acid to total metals in a range of 0.5:1 to 2:1.
9. The method for making a bi-functional catalyst of claim 8 , wherein the carboxylic binding acid comprises citric acid.
10. The method for making a bi-functional catalyst of claim 8 , wherein the carboxylic binding acid comprises sodium citrate.
11. A method for making a bi-functional catalyst suitable for catalytic oxidation oxides (NOx) contained in fuel combustion gases, comprising:
(a) providing an aqueous solution of adsorption function metal ions selected from the group consisting of barium (Ba) and lanthanum (La) for providing an adsorption function and adsorption sites in the bi-functional catalyst for adsorbing nitrogen oxides contained in combustion gases;
(b) providing an aqueous solution of oxidation function metal ions selected from the metals group consisting of copper (Cu) and manganese (Mn) for providing an oxidation function and oxidation sites in the bi-functional catalyst for oxidizing nitrogen oxides contained in combustion gases,
said absorption function metal ions having a molar ratio to the oxidation function metal ions in the range of 0.1:1 to 5:1;
(c) mixing said absorption and oxidation function metal ion solutions together and adding a binding agent acid having at least two functional groups for providing close intimate contact of said metal ions to form a precursor solution;
(d) drying said precursor solution and heating to a temperature of 500-800° C. (930-1470° F.) to form a metal oxide complex precursor material, then cooling the metal oxide complex precursor material; and
(c) forming a second solution of oxidation function metal ions comprising manganese (Mn) ions and a platinum (Pt) salt, and impregnating said metal oxide complex precursor material with the second solution, then drying and calcining the impregnated precursor material at 500-800° C. temperature and cooling to yield the bi-functional catalyst.
12. The method for making a bi-functional catalyst of claim 11 , wherein said adsorption function metal ions comprise barium (Ba).
13. The method for making a bi-functional catalyst of claim 11 , wherein said adsorption function metal ions comprise lanthanum (La).
14. The method for making a bi-functional catalyst of claim 11 , wherein said adsorption function metal ions comprise barium (Ba) and said oxidative function metal ions comprise copper (Cu) and manganese (Mn) promoted with platinum (Pt).
15. The method for making a bi-functional catalyst of claim 7 , including depositing the catalyst in powder form onto a porous support material.
16. A process for catalytic oxidation and removal of nitrogen oxides (NOx) contained in fuel combustion gases, the process comprising:
(a) providing a combustion gas stream containing nitrogen oxides (NOx) together with oxygen; and
(b) contacting said combustion gas stream with the bi-functional oxidation catalyst of claim 1 in order for said catalyst to adsorb and oxidize at least a portion of the nitrogen oxides (NOx) in said combustion gas stream at a temperature in a range of 170-550° F., a pressure in a range of 0.5-20 psig, and a space velocity in a range of 5,000-100,000 hr −1 to form higher oxides of nitrogen and thereby yield a treated combustion gas stream containing partially oxidized nitrogen oxides (NOx).
17. The catalytic oxidation process of claim 16 , wherein said combustion gas stream contains up to 0.5 vol. % nitrogen oxides (NOx).
18. The catalytic oxidation process of claim 16 , wherein said combustion gas stream in (b) has a temperature in a range 200-500° F., pressure in a range of 1-15 psig, and a space velocity in a range of 8,000-50,000 h −1 , and wherein the nitrogen oxides (NOx) in the treated combustion gas stream comprises at least about 50 vol % NO 2 .
19. The catalytic oxidation process of claim 18 , wherein the nitrogen oxides (NOx) in the treated combustion gas stream contains 60-98 vol % NO 2 .
20. The catalytic oxidation process of claim 16 , wherein said combustion gas stream contains up to 0.2 vol. % NOx.
21. The catalytic oxidation process of claim 16 , further comprising:
(c) contacting said treated gas stream containing partially oxidized nitrogen oxides (NOx) with a chemical oxidant having a molar ratio of said chemical oxidant to nitrogen oxides (NOx) in a range of 0.5:1 to 1.2:1 to further oxidize the partially oxidized nitrogen oxides (NOx) to higher oxides of nitrogen; and
(d) scrubbing the treated combustion gas stream containing the higher oxides of nitrogen with a scrubbing liquid to remove the higher oxides of nitrogen from the treated combustion gas and yield a further treated combustion gas stream containing less than about 15 ppm nitrogen oxides (NOx).
22. The catalytic oxidation process of claim 21 , wherein (c) is performed at a temperature in a range of 100-250° F. and a pressure in a range of 0.8-1.4 psig.
23. The catalytic oxidation process of claim 21 , wherein said chemical oxidant comprises ozone (O 3 ), and wherein the molar ratio of the ozone (O 3 ) to the nitrogen oxides (NOx) in said treated combustion gas stream is 0.8:1 to 1.0:1.
24. The catalytic oxidation process of claim 21 , wherein said scrubbing liquid comprises water.
25. The catalytic oxidation process of claim 21 , wherein (b) is performed at a temperature in a range of 300-350° F.
26. The catalytic oxidation process of claim 21 , wherein the further treated combustion gas stream formed in (d) contains less than about 10 ppm nitrogen oxides (NOx).
27. A bi-functional catalyst useful for oxidation and removal of nitrogen oxides (NOx) contained in fuel combustion gases, the catalyst comprising:
an absorption function metal oxide component comprising lanthanum oxide and optionally at least one other metal oxide selected from the group consisting of oxides of barium, cesium, strontium, and zirconium and providing adsorption function and adsorption sites for nitrogen oxides in fuel combustion gases; and
an oxidation function metal oxide component comprising at least one of copper or manganese promoted with platinum and optionally at least one other metal oxide selected from the group consisting of chromium, cobalt, iron, and platinum and providing an oxidation function and oxidation sites for nitrogen oxides in fuel combustion gases,
said adsorption metal oxide component and said oxidation metal oxide component being combined together in close intimate contact by means of an intermediate aqueous solution, comprising (i) at least type of adsorption function metal ions, (ii) at least one type of oxidation function metal ions, and (iii) a binding acid agent, that is heated and dried in order for said adsorption and oxidation metal oxide components to be chemically bonded closely together so as to form a metal oxide complex having a crystalline structure,
the molar ratio of the adsorption function metal ions to the oxidation function metal ions in the intermediate aqueous solution being in a range of 0.1:1 to 5:1.
28. A bi-functional catalyst useful for oxidation and removal of nitrogen oxides (NOx) contained in fuel combustion gases, the catalyst comprising:
an adsorption function metal oxide component comprising at least one metal oxide selected from the group consisting of oxides of barium, cesium, lanthanum, strontium, and zirconium; and
an oxidation function metal oxide component comprising at least one metal oxide selected from the group consisting of chromium, cobalt, copper, iron, manganese, and platinum,
said adsorption metal oxide component and said oxidation metal oxide component being combined together in close intimate contact so that said adsorption metal oxide component and said oxidation metal oxide component are chemically bonded closely together so as to form a metal oxide complex having a crystalline structure,
the molar ratio of metal in the adsorption function metal oxide component to metal in the oxidation function metal oxide component being in a range of 1:3 to 1:6.