Simultaneously removing sulfur and nitrogen oxides from gases
United States Patent McCrea et al.  
 [ Apr. 29, 1975 SIMULTANEOUSLY REMOVING SULFUR {54] 3.389.961 6/1968 Sundaresan et al 423/239 X AND NITROGEN OXIDES FROM GASES 3.498.743 3/1970 Kyllonen 423/239 3.502427 3/!970 Johswich 55/74 [76] In entors: onald cC ea. 1532 Tonopah 3.524.720 8/1970 Bauer 423/244 Ave., Pittsburgh, Pa. 15213; John 3.660940 5/1972 Harding et al. 423/239 G. Myers, 1600 Cumberland St., Pmsburgh 5205 Primary E.\&#39;aminerCharles Ni Hart 22 Filed; Man 2 1973 Assistant Examiner-Ferris H. Lander Altorney, Agent, or Firm-Roland H. Shubert; Gersten [21] Appl. No.: 337,342 Sadowsky [52] U.S. Cl. 55/68; 423/239; 423/244; [57] ABSTRACT 55/73; 55/74 [51] Int. Cl B01d 53/04 Hot flue gas cooled to and Passed Over 5 Field of Search 55 74 3 7 179 1 0 3 alkalized alumina Or alkali metal carbonate or oxide to 55/ 8 3 9 73 75; 423/239 244 simultaneously remove sulfur oxides and nitrogen OX- ides. Absorbent is regenerated by first heating to [56] References Cited 300-400C to drive off NO, and then heating to UNITED STATES PATENTS 6()0-700C to drive off absorbed sulfur compounds.  
 2,992,884 7/l96l Bienstock ct u]. 3. 423/244 4 Claims, 2 Drawing Figures Ll/5 zmcmosmnc 6A5 GAS ABSORBER PfiEC/P/TATOR S 645 I50 C COOLER I00 7&#39;0 IJOC&#39; SOL/D HEATER 4 300970 4000: --/vo T0 NITRIC 40/0 PRODUCT/0N 5 REGENERATION INCLUDING REDUCING GAS -----a SIMULTANEOUSLY REMOVING SULFUR AND NITROGEN OXIDES FROM GASES This invention relates to the removal of pollutants from waste gases.  
  Large amounts of sulfur oxides and nitrogen oxides are released to the atmosphere as a result of the com bustion of sulfur-containing coal and oil. Other sources of such emissions include water gases, smelter gases, petroleum and tar distillation gases, etc.  
  It is generally recognized that the release to the atmosphere of large amounts of sulfur oxides is highly undesirable and represents a major air pollution hazard. Further, it has come to be recognized that the release of nitrogen oxides to the atmosphere also constitues a hazard.  
  Many solid sorbents have been employed to remove sulfur oxides from waste gases. However, little work has been done on the removal of nitrogen oxides.  
  We have now discovered that certain solids sorbents, at a temperature of about 75-150C, will simultaneously remove sulfur oxides and nitrogen oxides from a waste gas, but nitrogen oxides are removed only when sulfur oxides are present in the gas. After absorption, the absorbent is heated to about 300400C to drive off NO which gas can then be treated in the prior art manner. Thereafter, the absorbent is heated to a temperature of about 600-700C to drive off and recover absorbed sulfur compounds.  
  It is therefore an object of the present invention to remove nitrogen oxides from waste gases.  
  Another object is to simultaneously remove sulfur oxides and nitrogen oxides from waste gases.  
 Another object is to partially convert S; to S0 A further object is to regenerate absorbent in a twostage heating process wherein nitrogen oxides are driven off in one stage and then sulfur compounds are driven off in a higher temperature second stage.  
  Other objects and advantages will be obvious from the following more detailed description of the invention taken in conjunction with the drawings in which:  
  FIG. 1 is a schematic of one embodiment of the present invention; and  
 FIG. 2 represents an alternative embodiment.  
  Referring to FIG. 1, flue gas from, for example, a coalor oil-burning power plant, normally at a temperature of about 150C, passes through an electrostatic precipitation step 1 to remove suspended particles such as fly ash. From there, the gas is passed through a cooling step 2 to cool the gas to about 75150, preferably 100-l30C, by prior art techniques such as water injection.  
  Thereafter the cooled gas is passed through absorbing step 3 having a bed composed of alkalized alumina, sodium or potassium carbonate or oxide or ores thereof (e.g. trona). Although impractical, oxides or carbonates of other metals in groups laof the periodic table can be employed.  
  The absorbent bed can be of any common type suitable for gas-solid contacting, such as fluidized bed, packed bed, or entrained reactor.  
  After the absorbent becomes spent, it is passed through two regenetion steps 4 and 5. In step 4, it is indirectly heated to 300400 to drive off NO. A small sweep stream of inert gas e.g. N may be used to sweep and collect NO. Gaseous NO is then converted to nitric acid in the prior art manner (e.g. to Ostwald process).  
  Next, the absorbent is heated at a higher temperature (600700C) in step 5 in the presence of a reducing gas such as hydrogen, reformed natural gas or producer gas, so as to ultimately produce H 8 off-gas and regenerated absorbent. The absorbent is then recycled to step 3. 1f the absorbent is alkalized alumina, step 5 is generally carried out at 60065 0C which drives off H 3.  
  With regard to absorbents of alkali metal carbonates or oxides, a heating temperature of 650700C is employed in step 5 which converts sulfates to sulfides (solid phase). Thereafter the absorbent is cooled to 400-500C in the presence of a mixture of H 0 and CO (approximately 1:1 mole ratio) which drives off H 8.  
  The following examples illustrate the advantages of the present invention:  
 EXAMPLE 1 Alkalized alumina having the following composition:  
 Component Weight, Percent A1 0 36.8 Na O 21.8 S l.() co 23.7 H 0 127 Component Volume, Percent S0 0.2147 (dry basis) NO 0.1091 (dry basis) CO 12.0 0 5.9 H 0 6.7 N, 75.1  
 The results of this experiment are shown in Table 1.  
 Table 1 Exit gas. S0 analyses Exit gas, NO analyses Time Vol. pct. Time Vol. pct.  
 (dry) (dry) 0.0 pct to 19 hr 30 min 0 hr 45 min 0.0004 19 hr 30 min 0.0019 2 hr 5 min .0007 20 hr 30 min 0.0126 3 hr 40 min .0081 21 hr 30 min 0.0305 6 hr 45 min .0089 22 hr 30 min 0.0545 7 hr 45 min .0117 8 hr 40 min .0142 10 hr 40 min .0152 13 hr 45 min .0133 14 hr 45 min .0167 15 hr 40 min .0197 17 hr 40 min .0200 20 hr 45 min .0499 21 hr 45 min .0591 23 hr 5 min .0763  
 As be seen from Table 1, more than percent of the S0 in the feed gas g/as removed for about 21 3. hours. More than 80 percent of the NO in the feed gas was&#39;removed for about 18 hours.  
 EXAMPLE 2 An experiment, identical to Example 1, was conducted except the gas and solid were maintained at 130C. The feed gas contained 0.151 1 vol. percent S and 0.1003 vol. percent NO. Results of this experiment are shown in Table 2.  
 Table 2 SO: analyses NO, analyses Time Vol. pct. Time Vol. pct.  
 (d y) (dry) 0.0 pet to 20 hr 40 min 1 hr 0 min .0015 20 hr 40 min .0201 5 hr 0 min .0093 21 hr 40 min .0322 7 hr 0 min .0144 10 hr0min .0181 13 hr 0 min .0298 17 hr 30 min .0367 20 hr 30 min .0545  
 Removal of S0 was similar to Example 1. NO removal, however, had fallen below 80 percent after 13 hours.  
 EXAMPLE 3 An experiment, identical to Example 1, was conducted except the gas and solid were maintained at 160C. The feed gas contained 0.2225 volume percent S0 and 0.1072 volume percent NO. Results are shown in Table 3.  
 Removal of $0 was similar to Examples 1 and 2. Removal of as much as 80 pct of the NO was never achieved.  
 EXAMPLE 4 Table 4 sO analyscs NO, analyses Time Vol. pct Time Vol. pct.  
 (dry) (dry) 2hr 20 min .0112 1 hr 10 min @0210 Table 4-Continued S0 analyses NO analyses Time Vol. pct Time Vol. pct.  
 (dry) ry) 6 hr 0 min .0065 3 hr 10 min .0232 4 hr 40 min .0274  
 As can be seen from Table 4, substantial removal of S0 and NO was achieved.  
 EXAMPLE 5 A sample of Trona was crushed, then heated to C in air for 48 hours. After this treatment it contained 2.3 wt pct NaHCO and 87.9 wt pct Na CO An experiment identical to Example 1 was conducted. The feed gas contained 0.2219 vol pct S0 and 0.1085 vol pct NO. Results of the experiment are tabulated in Table 5.  
 Table 5 S0 analyses NO, analyses Time Vol. pct. Time Vol. pct.  
 (dry) (dry) 0.0 pet to 23 hr 30 min 0 hr 45 min 0.0042 23 hr 30 min 0.0089 2 hr 5 min 0.0122 24 hr 30 min .0748 6 hr 45 min 0.0161 9 hr 05 min 0.0125 13 hr 45 min 0.0195 16 hr 15 min 0.0186 17 hr 50 min 0.0286 20 hr 55 min 0.0449  
 Removal of both S0 and NO was essentially identical to Example 1.  
 EXAMPLE 6 After completion of the experiment described in Example l, the absorbent was heated to 300C and N passed over it at a rate of 0.1 scfh. The NO concentration in the exit gas averaged 1.28 vol pct during one hour operation. Analysis by mass spectrometry showed that NO was the only oxide of nitrogen in the gas.  
 EXAMPLE 7 Trona ore which had been saturated with S0 and NO and contained 8.4 wt pct as Na SO was heated to 700C and contacted with H for 60 minutes. During the experiment 37.6 wt pct of the initial sulfur was converted to Na s, 5.9 wt pct was liberated and 56.5 pct remained as Na SO The material was then contacted with a mixture of CO and steam, in a mo] ratio of approximately 1 to 1 for minutes at 400C. Of the sulfur remaining after the hydrogen reduction, 33.8 pct was liberated. This result shows that almost all of the sulfur converted to a sulfide by reduction can be removed by contact with steam and CO To remove NO from the gas, the presence of S0 is most essential, as shown by the following:  
 EXAMPLE 8 The experiment of Example 5 was repeated except the gas and solid were maintained at 130C and the simulated flue gas was S0 free. The feed gas contained 0.1017 vol pct NO. Analyses of the exit gas were taken over a 6 hour period. The average of 8 analyses was 0.0993 vol pct NO,. in the exit gas.  
 EXAMPLE 9 The experiment of Example 8 was repeated except that the simulated flue gas contained about 0.02 vol pct S0 and 0.1073 vol pct NO. Analyses of the exit gas were taken over a 7 hour period. The average of 4 analyses was 0.1034 vol pct NO... Comparison with Example 2 shows that the minimum S0 concentration needed to absorb NO falls between 0.02 and 0.15 vol pct.  
  It is believed that a catalytic reaction between NO and S0 occurs in the presence of the absorbent of the present invention which reaction produces N0 and that the N0 is then readily removed by the absorbent. The following example illustrates the ready removal of N02.  
 EXAMPLE 10 An experiment identical to Example 1 was conducted except the feed gas composition was.  
 Component Vol. pct.  
 NO 0.5600 (dry basis) N; 86.8 2 5.9 H 0 6.7  
  Analyses of NO in the exit gas during a 6 hour test are tabulated in Table 10.  
  As can be seen from Table 10, substantial amounts of NO, are removed by the absorbent.  
 In addition to formation of N0 S0 is another intermediate formed during the process. Tests have shown that reducing the gas-absorbent contact time produces an exit gas having an increased S0 content. Since it is well-known in the art that the presence of S0 in a flue gas improves electrostatic percipitator performance, the alternative embodiment shown in FIG. 2 may be employed in the practice of the present invention.  
  Referring to P16. 2, flue gas from, for example, a coal-burning power plant is conveyed by conduit 6 to electrostatic precipatator 7. A minor portion of the gas in conduit 6 is tapped off by conduit 8 and passed through gas cooler 9 to reduce the temperature to about 100-130C. From there, the gas is passed via conduit 10 to a tubular reactor 11. Absorbent is injected through conduit 12 into the reactor. The absorbent is then carried with the gas through conduit 13 back into main conduit 6, and is finally collected with other particulates in electrostatic precipitator 7. The quantity of flue gas treated with absorbent is selected so that the gas entering the electrostatic precipitator contains 10 to 15 ppm S0 Typically, 1 2 vol of the total flue gas is treated in this manner.  
 What is claimed is:  
  1. A process for removing nitrogen oxides, selected from the group consisting of NO and N0 from a gas which contains at least 200 ppm of sulfur dioxide which comprises contacting said gas at a temperature of about l50C. with a solid absorbent selected from the group consisting of alkalized alumina, sodium, and potassium carbonate or oxide. recovering nitrogen oxides from said absorbent by heating it to a temperature of 300400C and thereafter regenerating said absorbent to a temperature of 600-700C in the presence of a reducing gas whereby sulfur compounds are removed from the absorbent.  
  2. The process of claim 1 wherein said contacting temperature is about C.  
  3. The process of claim 1 wherein said gas is produced by burning coal or oil.  
 4. The process of claim 3 wherein said contacting temperature is about 100 130C.