Abstract:
The present invention provides a nitrogen dioxide absorbent for the exhaust gas purifying facility designed to remove by absorption or adsorption of NO 2  from a gas (such as ventilation gas from road tunnels) containing NO x  in low concentrations. The absorbent is composed of a porous carrier and a basic amino acid and/or organic amine compound supported thereon. The absorbent is produced by impregnating a porous carrier sequentially with two aqueous solutions each containing in an amount of, for example, 0.5-3.0 mol/l (preferably 1.0-2.0 mol/l) of basic amino acid and 0.5-3.0 mol/l (preferably 1.0-2.0 mol/l) of organic amine compound, or impregnating a porous carrier with a solution containing 0.5-3.0 mol/l (preferably 1.0-2.0 mol/l) of basic amino acid and/or 0.5-3.0 mol/l (preferably 1.0-2.0 mol/l) of organic amine compound.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a nitrogen dioxide (NO 2 ) absorbent or adsorbent for automotive exhaust gas purifying facilities to remove NO 2  by absorption or adsorption from ventilation gas discharged from road tunnels which contains nitrogen oxides (NO x ) in low concentrations. 
     2. Description of the Related Art 
     A conceivable common way of removing by absorption NO 2  (which is an acidic gas) from NO x -containing gas is by reaction with alkali for fixation into nitrate or nitrite. In actual practice, however, very little NO 2  is absorbed when air containing several ppm of NO 2  is bubbled in an aqueous solution of KOH. 
     In contrast, NO 2  in very low concentrations as above can be absorbed and removed effectively by the use of a solid absorbent consisting of a porous carrier (such as titania or alumina which has solid acid properties) and KOH impregnated into and supported on the carrier, which had previously been proposed by the present inventors. (See Japanese Patent Laid-open No. 211427/1998.) 
     The present inventors studied in detail the nitrogen dioxide absorbent composed of a carrier of solid acid or activated carbon and a hydroxide of strong alkali (such as K and Na) supported thereon. As the result, they found the following problems involved in it. 
     In the ase of a carrier of solid acid: 
     (1) A nitrogen dioxide absorbent composed of a carrier of solid acid and a hydroxide of strong alkali (such as K and Na) supported thereon is low in absorption rate unless NO x  contain s nitrogen monoxide (NO) in an amount equal to or more than NO 2 . See FIG.  1 . 
     (2) If NO x  contains NO in an amount equal to or more than NO 2 , the absorbing rate of NO 2  is approximately linearly proportional to its concentration at 10 ppm or above. (Incidentally, the absorbing rate of NO is constant regardless of its concentration under the same absorbing condition.) However, in concentrations at 5 ppm or below, the absorbing rate of NO 2  begins to decrease with decreasing concentration; it is very low at 1 ppm or below. This tendency becomes remarkable according as more NO 2  is accumulated in the absorbent. See FIG.  2 . 
     (3) If NO x  contains NO in an amount equal to or more than NO 2  and if NO x  is not accumulated initially in large amounts on the surface of the absorbent, NO and NO 2  are absorbed almost equally and hence the absorbent is rapidly consumed. 
     In the case of a carrier of activated carbon: 
     (4) Activated carbon (well known as an adsorbent of NO 2 ) adsorbs NO 2  alone and adsorbs and absorbs NO 2  efficiently even in the absence of NO. However, its absorbing rate decreases at 1 ppm or below according as the accumulated amount of NO 2  increases. 
     (5) Activated carbon releases as much NO as one-half to one-quarter the amount of NO 2  adsorbed. 
     (6) An absorbent composed of activated carbon and a strong alkali hydroxide supported thereon absorbs NO and NO 2  almost equally in the initial stage, like an absorbent employing an acid solid as the carrier; however, its absorbing rate of NO decreases according as the accumulated amount of NO x  increases on the surface of the absorbent. After a large amount of NO x  has accumulated, it reversibly releases as much NO as one-half to one-quarter the amount of NO 2  absorbed. This results in an increase in NO concentration in the gas phase. See FIG.  3 . 
     The present inventors have interpreted these phenomena as follows. 
     (1) NO 2  in low concentrations does not react directly with alkali. 
     (2) At first, NO 2  is adsorbed to the carrier. The adsorbed NO 2  then changes into a compound which readily reacts with alkali. Finally, this compound reacts with alkali for its fixation. 
     (3) Presumably, the compound in (2) readily reactive with alkali is N 2 O 3  in the case of solid acid carrier supporting strong alkali, and it is N 2 O 4  in the case of activated carbon carrier supporting strong alkali. 
     
       
         NO+NO 2 →N 2 O 3    
       
     
     
       
         2NO 2 →N 2 O 4    
       
     
     (4) In either case, those compounds in (3) decompose into nitric acid or nitrate (which is stable) and nitrous acid or nitrite (which is unstable). 
     
       
         N 2 O+2MOH→2MNO 2 +H 2 O  
       
     
     
       
         N 2 O 4 +2MOH→MNO 3 +MNO 2 +H 2 O  
       
     
     (where, M: alkali metal) 
     (5) The nitrous acid or nitrite is oxidized into nitric acid or nitrate (which is stable) or decomposed into NO, which is released. 
     
       
         2MNO 2 +O 2 →2MNO 3    
       
     
     
       
         2MNO 2 +H 2 O→NO 2 +2MOH+NO (released)  
       
     
     (6) Usually, strong alkali nitrite is not readily decomposed but is oxidized into nitrate, and weak alkali nitrite is readily decomposed into NO. 
     It is concluded from the foregoing discussion that a d esirable nitrogen dioxide absorbent should meet the following requirements. 
     (a) The absorbent should have a catalytic action to denature NO 2  into a compound readily reactive with alkali. 
     (b) The absorbent should have alkali densely arranged around the active site of the catalyst in (a) so that the denatured product of NO 2  reacts with alkali. 
     (c) The resulting alkali nitrate and nitrite in (b) should have moderate stability so that it fixes the adsorbed NO 2  in a stable manner and permits it to diffuse rapidly outward from the vicinity of the active site for NO 2  denaturation in (a). 
     The concept mentioned above is depicted in FIG.  4 . 
     NO 2  in the gas phase is adsorbed at the active sites of the catalyst and is denatured there into a form readily reactive with alkali. The denatured product rapidly reacts with alkali hydroxide near the active site, and the resulting nitrate and nitrite are retained stably. The active site of the catalyst becomes vacant, and the cycle of adsorption-denaturation can be repeated. 
     The thus formed nitrate or nitrite has its anions (NO 3   −  or NO 2   − ) dispersed into the vicinity from near the active site. Thus free alkali is regenerated near the active site, and it repeats its reaction with the denatured product forming at the active site. 
     At an early time when the absorption of NO 2  has just begun, alkali is present in large amounts near the active site and hence the rate of absorption is limited by the rate of absorption of NO 2  to the active site. Accordingly, as the amount of NO 2  absorbed increases, the rate of absorption is limited by the rate of diffusion into the vicinity of the active site. 
     The present inventors had previously proposed a carrier of titania (TiO 2 ) impregnated with a manganese (Mn) salt, followed by drying and firing. This carrier meets the requirement of (a), or it has a catalytic action for denaturation of NO 2 . See Japanese Patent Laid-open No. 192049/1996. 
     The present inventors had also proposed a nitrogen dioxide absorbent employing a carrier impregnated with a hydroxide of alkali metal (such as K and Na). See Japanese Patent Laid-open No. 211427/1998. 
     The above-mentioned absorbent was capable of efficient absorption of NO 2  in low concentrations (1 ppm or below). This was a remarkable improvement as expected. However, it was found that the rate of absorption of NO 2  in low concentrations rapidly decreases according as NO 2  accumulates on the surface of the absorbent. See FIG. 5. A probable reason for this is that strong alkali nitrate or nitrite is so stable that it does not permit its anions (NO 2   −  or NO 3   − ) to readily diffuse from near the active site, with the result that free alkali rapidly decreases near the catalytic active site. 
     SUMMARY OF THE INVENTION 
     The present inventors looked for an alkali which meets the requirement of (c). As the result, they found that desired characteristic properties are obtained by a basic amino acid, particularly arginine, and an organic amine compound, particularly guanidine. 
     It is an object of the present invention to provide a nitrogen dioxide absorbent which comprises a porous carrier and a basic amino acid and/or organic amine compound supported thereon. 
     According to the present invention, the nitrogen dioxide absorbent is produced by a process which comprises impregnating a porous carrier sequentially with two aqueous solutions each containing a basic amino acid, for example, in an amount of 0.5-3.0 mol/l, preferably 1.0-2.0 mol/l, and an organic amine compound in an amount of 0.5-3.0 mol/l, preferably 1.0-2.0 mol/l, or with one aqueous solution containing a basic amino acid in an amount of 0.5-3.0 mol/l, preferably 1.0-2.0 mol/l, and/or an organic amine compound in an amount of 0.5-3.0 mol l, preferably 1.0-2.0 mol/l. 
     According to the present invention, impregnation is followed by drying at a temperature of 150° C. or below, preferably 100° C. or below. 
     It is another object of the present invention to provide a nitrogen dioxide absorbent which preferably comprises a porous carrier and a basic amino acid and organic amine compound and/or alkali hydroxide supported thereon. 
     According to the present invention, the nitrogen dioxide absorbent is also produced by a process which comprises impregnating a porous carrier with an aqueous solution containing a basic amino acid in an amount of, for example, 0.5-2.0 mol/l, preferably 0.8-1.5 mol/l, an organic amine compound in an amount of 0.5-3.0 equivalents, preferably 0.8-2.0 equivalents (based on the carboxylic acid of the amino acid), and/or an alkali hydroxide in an amount of 0.5-3.0 equivalents, preferably 0.8-2.0 equivalents (based on the carboxylic acid of the amino acid). 
     According to the present invention, impregnation is followed by drying at a temperature of 150° C. or below, preferably 100° C. or below. 
     According to the present invention, the porous carrier is a porous oxide having solid acid properties. The porous oxide having solid acid properties includes, for example, alumina, silica•alumina, titania, and zeolite. They can be used alone or in combination with one another. 
     A preferred example of the porous carrier is a porous oxide carrying one or more metals selected from the group consisting of Mn, Co, Fe, and Ni. It is produced by impregnating a porous oxide with an aqueous solution containing (or solutions each containing) inorganic acid salts (excluding sulfates) or organic acid salts of said metals in an amount of 0.5-5 mol/l, preferably 2-4 mol/l, at one time or sequentially. 
     The porous oxide should have a specific surface area of 30-500 m 2 /g, preferably 60-120 m 2 /g. 
     The porous oxide can be held in interstices between fibers of preform in the form of plate or honeycomb. 
     Another preferred example of the porous carrier is activated carbon. This activated carbon should have a specific surface area of 100-2000 m 2 /g, preferably 300-600 m 2 /g. 
     In addition, the activated carbon should preferably be in the form of a honeycomb. 
     According to the present invention, the basic amino acid should preferably be arginine, and the organic amine compound should preferably be guanidine. The alkali hydroxide should preferably be one or more than one member selected from lithium hydroxide, potassium hydroxide, and sodium hydroxide. 
     The nitrogen dioxide absorbent constructed as mentioned above is suitable for purification of ventilation gas discharged from road tunnels. It is capable of absorbing and removing NO 2  from ventilation gas passing at a flow rate of 0.05-10.0 Nm/s (in terms of superficial velocity). 
     A detailed description of the nitrogen dioxide absorbent in the present invention follows. 
     The reaction of an organic amine compound with NO 2  has long been known. This knowledge has been applied to a nitrogen dioxide absorbent composed of activated carbon and an aromatic (organic) amine compound having a low vapor pressure supported thereon. In addition, the reaction of ethanolamine with NO 2  is used for the analysis of nitrogen dioxide in air (known as “alkali filter paper method”). 
     Unfortunately, since an organic amine compound bonds to a carrier only weakly and vaporizes slightly, there has been no practical absorbent which withstands prolonged use (up to several months or one year) for a large amount of gas. 
     In order to address the above-mentioned problems, the present inventors have developed a new nitrogen dioxide absorbent composed of a carrier of solid acid or activated carbon having an additional denaturing catalytic action on NO x  and a basic amino acid or guanidine supported thereon which is solid at normal temperature and has a very low vapor pressure. The basic amino acid or guanidine bonds strongly to a solid acidic oxide as the carrier and becomes adsorbed strongly by activated carbon. 
     The nitrogen dioxide absorbent of the present invention is composed of a carrier of solid acid or activated carbon and a basic amino acid or guanidine supported thereon. It functions as an excellent nitrogen dioxide absorbent which can be used under severe conditions as mentioned above. 
     The above-mentioned nitrogen dioxide absorbent as such is of practical use; however, the present inventors have found a way to improve its performance further. 
     An amino acid usually has an amino group (basic) and a carboxyl group (acid). The former serves to fix NO 2 , but the latter does not. On the other hand, both arginine and guanidine have an imido group (HN═C), which, like an amino group, reacts with the solid acid site, thereby helping arginine and guanidine to be fixed to the carrier surface. This results in an increase in free amino groups useful for the fixing of NO 2 . Arginine and guanidine vaporize less than other organic amine compounds and hence are highly capable of fixing NO 2 . 
     The carboxyl group in arginine is close to the amino group as the structural formula [I] shows below. It does not serve to fix NO 2 , but it also prevents the diffusion of NO 3   − , NO 2   − , etc. from one amino group to another.                           
     Upon reaction with a basic compound, this carboxyl group effectively fixes NO 2 , thereby increasing the absorbing capacity of the absorbent. Especially, guanidine (shown by the formula [II] below) as the basic compound provides only amino groups useful for the diffusion of NO 2 ; therefore, it reduces the factor to prevent the diffusion.                           
     The easy diffusion of NO 2  not only increases the rate of absorption of NO 2  but also helps to fix NO 2  in the broader area around the catalytic active site. This leads to an increase in absorbing capacity. 
     The foregoing is illustrated in FIG.  6 . 
     According to a preferred embodiment, preferred nitrogen dioxide absorbent is obtained by preparing a titania carrier incorporated with Mn and then impregnating the carrier with an aqueous solution containing arginine and alkali hydroxide or guanidine in approximately equimolar amounts, followed by drying. In practice, however, the alkali hydroxide or guanidine should be used in an amount slightly more than arginine because it reacts directly with the acid site of the carrier. 
     The absorbing capacity for NO 2  increases with the increasing amount of arginine supported; however, an excess amount of arginine clogs the pores of the catalyst and covers the active site of the catalyst, thereby decreasing the absorbing rate. 
     Both activated carbon and solid acid produce almost the same effect when used as the carrier for the nitrogen dioxide absorbent. The effect produced by the addition of arginine is lower than this. 
     In general, as compared with solid acid as the carrier, activated carbon has a larger specific surface area but a smaller pore diameter and hence a lower critical supporting amount (per specific surface area) which does not lower the absorbing rate. 
     The nitrogen dioxide absorbent of the present invention exhibits its essential functions by virtue of: 
     (1) the solid acid carrier or activated carbon carrier provided with the denaturing catalytic action on NO x , and 
     (2) the basic amino acid and organic amine compound or alkali hydroxide supported on the carrier. 
     Therefore, its performance is not greatly affected by the carrier&#39;s fine surface structure (such as crystal form, pore distribution, acidity, surface electron density distribution, and oxide surface coordination number), nor is it essentially affected by the type of basic amino acid and organic amine compound used. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 is a graph showing the relation between the NO 2 /NO x  ratio and the NO 2  removal ratio. 
     FIG. 2 is a graph showing the relation between the NO 2  concentration at the entrance and the NO 2  removal ratio. 
     FIG. 3 is a graph showing the relation between the adsorption time and the concentrations of NO and NO 2 . 
     FIG. 4 is a conceptual diagram showing the absorption of NO 2  on the surface of the nitrogen dioxide absorbent. 
     FIG. 5 is a graph showing the relation between the NO 2  concentration at the entrance and the NO 2  removal ratio. 
     FIG. 6 is a conceptual diagram showing the postulated surface structure of the nitrogen dioxide absorbent. 
     FIG. 7 is a graph showing the relation between the amount of NO 2  absorption and the ratio of NO 2  absorption. 
     FIG. 8 is a graph showing the relation between the amount of NO 2  absorption and the ratio of NO 2  absorption. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The following examples demonstrate the production and the performance and characteristic properties of the nitrogen dioxide absorbent according to the present invention. 
     In the following examples, titania is used as the solid acid carrier and pitch-based activated carbon is used as the activated carbon; however, the use of these carriers is not intended to limit the nitrogen dioxide absorbent of the present invention. 
     EXAMPLE 1 
     (a) Preparation of nitrogen dioxide absorbent in lamellar form based on a solid acid carrier: 
     A piece of ceramics paper (0.5 mm thick, made by Nippon Muki Co., Ltd.) was immersed in a 34% by weight colloidal solution of titania (TiO 2 ) as solids, followed by drying at 120° C. in the air. This step permits titania to be held in interstices between ceramics fibers constituting the ceramics paper. 
     After repeating the above-mentioned step, there was obtained a lamellar solid acid carrier composed of ceramics paper and anatase-type titania supported thereon. 
     The amount of titania in this lamellar carrier was 420 g/m 2  (per basis weight of paper). 
     The carrier was then immersed in an aqueous solution containing 3.0 mol/l of manganese nitrate (Mn(NO 3 ) 2 ) for 30 minutes, followed by drying at 120° C. in the air and firing at 400° C. for 3 hours in an air stream. Thus there was obtained a lamellar carrier carrying Mn and having the NO 2 -modified catalytic activity. The amount of Mn supported on this carrier was 3.2 mmol/g (TiO 2 ) and the specific surface area was 87 m 2 /g. 
     The above-mentioned carrier was immersed in an aqueous solution of L-arginine (1.3 mol/l) and guanidine (1.5 mol/l) for 30 minutes, followed by drying at 60° C. in an air stream. Thus there was obtained a nitrogen dioxide absorbent (A) in lamellar form. 
     (b) Performance of nitrogen dioxide absorbent based on a solid acid carrier: 
     Two pieces of the absorbent (A) in lamellar form (100 mm×35 mm) were placed in an absorbing tube. A standard gas of the composition shown in Table 1 was passed through the absorbing tube at a flow rate of 2 l/min. 
     
       
         
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
             
             
               
                   
                 NO 
                  1.2 ppm 
               
               
                   
                 NO 2   
                 0.12 ppm 
               
               
                   
                 Relative humidity 
                 60% 
               
               
                   
                 Air 
                 Remainder  
               
               
                   
                   
               
             
          
         
       
     
     The inflow and outflow gases were sampled and analyzed for NO 2  concentration. The rate of NO 2  absorption was calculated by the equation below. 
     
       
         Rate of NO 2  absorption=(A−B)/A×100  
       
     
     where, 
     A: concentration of NO 2  in inflow gas, and 
     B: concentration of NO 2  in outflow gas. 
     This measurement was carried out for a predetermined time. Subsequently, an accelerating gas of the composition shown in Table 2, which contains a large amount of NO 2 , was passed through the absorbing tube for a predetermined time. The rate of NO 2  absorption was calculated and the cumulative amount of absorption was measured. 
     
       
         
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
             
             
               
                   
                 NO 
                 50.0 ppm 
               
               
                   
                 NO 2   
                 30.0 ppm 
               
               
                   
                 Relative humidity 
                 60% 
               
               
                   
                 Air 
                 Remainder  
               
               
                   
                   
               
             
          
         
       
     
     After that, the standard gas was passed again, and the rate of NO 2  absorption in the low concentration region was measured. 
     This procedure was repeated four times, and the relation between the amount of NO 2  absorption and the rate of NO 2  absorption was obtained. The results are shown in FIG.  7 . 
     It is noted from FIG. 7 that the rate of absorption remained at almost 100% until the amount of NO 2  absorption reached 5 l/m 2  after the start of absorption, and the rate of absorption decreased to about 90% when the amount of absorption reached 7 l/m 2 . 
     EXAMPLE 2 
     (a) Preparation of nitrogen dioxide absorbent in honeycomb form based on an activated carbon carrier: 
     A honeycomb of activated carbon made by Takeda Chemical Industries, Ltd., which had been dried at 80° C. in the air, was immersed in an aqueous solution containing 0.8 mol/l of guanidine for 30 minutes, followed by drying at 60° C. Thus there was obtained a nitrogen dioxide adsorbent (B) in honeycomb form based on activated carbon carrier supporting guanidine. 
     This adsorbent (B) has a specific surface area of 490 m 2 /g. 
     (b) Performance of nitrogen dioxide adsorbent based on an activated carbon carrier: 
     The nitrogen dioxide adsorbent (B) was cut into pieces, each measuring 20 mm×20 mm×50 mm, and they were placed in an absorbing tube. A standard gas of the composition shown in Table 1 was passed through the absorbing tube at a flow rate of 6 l/min. 
     Subsequently, the same procedure as (b) in Example 1 was repeated to obtain the relation between the amount of NO 2  absorption and the rate of NO 2  absorption. The results are shown in Table 8. 
     It is noted from FIG. 8 that, as in Example 1, the rate of absorption remained at almost 100% until the amount of NO 2  absorption reached 5 l/m 2  after the start of absorption, and the rate of absorption decreased to about 90% when the amount of absorption reached about 10 l/m 2 . 
     EXAMPLE 3 
     Nitrogen dioxide absorbent based on a metal-containing carrier, and performance of modified catalyst: 
     The same procedure as (a) in Example 1 was repeated to give nitrogen dioxide absorbents (C) to (I), except that the metal salt added was changed by those shown in Table 3. 
     
       
         
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                   
                   
                 Amount of TiO 2   
                   
               
               
                   
                   
                 Amount added 
                 Specific surface 
                 supported (g/m 2 ) 
                 Rate of NO 2   
               
               
                 Code 
                 Metal salt added 
                 (mmol/g TiO 2 ) 
                 area (m 2 /g) 
                 (basis weight) 
                 absorption 
               
               
                   
               
             
             
               
                 A 
                 Manganese nitrate 
                 3.2 
                 87 
                 420 
                 80 
               
               
                 C 
                 Manganese chloride 
                 3.5 
                 82 
                 395 
                 75 
               
               
                 D 
                 Manganese nitrate 
                 2.0 
                 94 
                 402 
                 76 
               
               
                 E 
                 Manganese nitrate 
                 4.5 
                 80 
                 435 
                 78 
               
               
                 F 
                 Cobalt nitrate 
                 3.0 
                 85 
                 415 
                 78 
               
               
                 G 
                 Iron (II) nitrate 
                 2.9 
                 89 
                 414 
                 79 
               
               
                 H 
                 Nickel nitrate 
                 3.2 
                 85 
                 420 
                 79 
               
               
                 I 
                 Magnesium nitrate 
                 3.1 
                 88 
                 418 
                 28 
               
               
                 J 
                 None 
                 — 
                 118  
                 418 
                 25 
               
               
                   
               
             
          
         
       
     
     Each of the nitrogen dioxide absorbents (C) to (I), measuring 100 mm×35 mm, was placed in an absorbing tube. A standard gas of the composition shown in Table 1 was passed through the absorbing tube at a flow rate of 4 l/min, and the rate of absorption (initial performance) was measured. The results are shown in Table 3. It is noted that magnesium nitrate does not contribute to the rate of NO 2  absorption. 
     EXAMPLE 4 
     Synergistic effect of arginine and organic amine compound and/or alkali hydroxide (in the case of solid acid carrier) 
     The lamellar carrier incorporated with Mn in Example 1 was given arginine and organic amine compound and/or alkali hydroxide in different concentrations (as shown in Table 4). Using this carrier, there were obtained nitrogen dioxide absorbents (K) to (T) in the same manner as in Example 1. These absorbents were tested for performance in the same manner as (b) in Example 1. Table 4 shows examples of concentrations of immersion solutions and NO 2  absorption performance. 
     
       
         
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
             
             
               
                   
                   
               
               
                   
                 Concentration of solution (mol/l) 
                 NO 2  absorption (%) 
               
             
          
           
               
                 Code 
                 Arginine 
                 Guanidine 
                 KOH 
                 NaOH 
                 LiOH 
                 Initial 
                 After absorption of NO 2  (7 l/m 2 ) 
               
               
                   
               
               
                 K 
                 0.8 
                 1.0 
                 — 
                 — 
                 — 
                 100 
                 73 
               
               
                 L 
                 1.3 
                 1.0 
                 — 
                 — 
                 — 
                 100 
                 88 
               
               
                 M 
                 1.3 
                 2.0 
                 — 
                 — 
                 — 
                  98 
                 91 
               
               
                 N 
                 2.0 
                 2.2 
                 — 
                 — 
                 — 
                  96 
                 93 
               
               
                 O 
                 1.3 
                 — 
                 1.5 
                 — 
                 — 
                 100 
                 85 
               
               
                 P 
                 1.3 
                 — 
                 — 
                 1.5 
                 — 
                 100 
                 84 
               
               
                 Q 
                 1.3 
                 — 
                 — 
                 — 
                 1.5 
                 100 
                 85 
               
               
                 R 
                 2.0 
                 — 
                 — 
                 — 
                 — 
                 100 
                 48 
               
               
                 S 
                 — 
                 2.0 
                 — 
                 — 
                 — 
                 100 
                 42 
               
               
                 T 
                 — 
                 — 
                 2.0 
                 — 
                 — 
                 100 
                 30 
               
               
                   
               
             
          
         
       
     
     EXAMPLE 5 
     Synergistic effect of arginine and organic amine compound and/or alkali hydroxide (in the case of activated carbon carrier) 
     The activated carbon carrier was given arginine and organic amine compound and/or alkali hydroxide in the same way as in Example 2. Thus there were obtained nitrogen dioxide absorbents (AC-1) to (AC-7). They were tested for performance. (The samples were cut into smaller pieces, each measuring 20 mm×20 mm×25 mm, so that the rate of NO 2  absorption was low.) The results are shown in Table 5. 
     
       
         
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 5 
               
             
             
               
                   
                   
               
               
                   
                 Concentration of solution (mol/l) 
                 NO 2  absorption (%) 
               
             
          
           
               
                 Code 
                 Arginine 
                 Guanidine 
                 KOH 
                 NaOH 
                 Initial 
                 After absorption of NO 2  (7 l/m 2 ) 
               
               
                   
               
               
                 AC-1 
                 0.6 
                 — 
                 — 
                 — 
                 65 
                 42* 
               
               
                 AC-2 
                 0.8 
                 — 
                 — 
                 — 
                 60 
                 40* 
               
               
                 AC-3 
                 1.0 
                 — 
                 — 
                 — 
                 57 
                 38* 
               
               
                 AC-4 
                 — 
                 0.6 
                 — 
                 — 
                 74 
                 58* 
               
               
                 AC-5 
                 — 
                 0.8 
                 — 
                 — 
                 75 
                 65* 
               
               
                 AC-6 
                 — 
                 1.0 
                 — 
                 — 
                 70 
                 66  
               
               
                 AC-7 
                 — 
                 0.8 
                 0.2 
                 — 
                 71 
                 61  
               
               
                   
               
               
                 *discharged NO (equivalent to 1/2 to 1/4 of NO 2  absorbed)  
               
             
          
         
       
     
     EXAMPLE 6 
     Synergistic effect of arginine and organic amine compound and/or alkali hydroxide (in the case of granular carrier) 
     Each of solid acid granular carriers (8 to 14 mesh in size) was immersed in an aqueous solution containing 3.0 mol/l of manganese nitrate for 30 minutes, followed by drying at 120° C. in the air for 3 hours and firing at 400° C. for 5 hours. Thus there were obtained solid acid carriers incorporated with manganese. They were immersed in an aqueous solution containing 1.3 mol/l of L-arginine and 1.5 mol/l of guanidine for 30 minutes, followed by drying at 60° C. in the air for 5 hours. There were obtained nitrogen dioxide absorbents in granular form (PP-1) to (PP-7). 
     4 ml each of these absorbents was placed in an absorbing tube. A standard gas of the composition shown in Table 1 was passed through the absorbing tube at a flow rate of 2 l/min, and the inflow and outflow gases were analyzed for NO 2  concentration to determine the initial performance. Then, an accelerating gas of the composition shown in Table 2 was passed until the absorption of NO 2  reached 250 ml. At that point the accelerating gas was switched back to the standard gas, and the performance after NO 2  absorption was determined. The results are shown in Table 6. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                   
                   
                 Specific surface 
                 Amount of Mn 
                 Absorption of NO 2  (%) 
               
             
          
           
               
                 Code 
                 Carrier 
                 area (m 2 /g) 
                 added (mmol/g) 
                 Initial 
                 After absorption of 250 ml/g 
               
               
                   
               
               
                 PP-1 
                 Titania 
                 72.6 
                 — 
                 72.5 
                 61.0 
               
               
                 PP-2 
                 Titania 
                 72.6 
                 0.58 
                 100 
                 79.9 
               
               
                 PP-3 
                 γ-alumina 
                 123 
                 — 
                 78.8 
                 65.2 
               
               
                 PP-4 
                 γ-alumina 
                 123 
                 0.82 
                 100 
                 70.2 
               
               
                 PP-5 
                 Silica-alumina 
                 511 
                 0.85 
                 100 
                 77.0 
               
               
                 PP-6 
                 Zeolite 
                 425 
                 0.85 
                 100 
                 82.1 
               
               
                 PP-7 
                 Activated 
                 1350 
                 — 
                 100 
                  87.5* 
               
               
                   
                 carbon