Abstract:
A novel method is described whereby chlorine dioxide is produced through the chemical reduction of ammonium chlorate in an aqueous acidic solution. The reduction reaction takes place at elevated temperatures with or without a catalyst. The reducing agent of this reaction is preferably hydrogen peroxide, glycerol, or sucrose. Chlorine dioxide may be produced in accordance with this invention at a substantially higher rate and in higher yield than with conventional methods using sodium chlorate. Further, the chlorine dioxide produced is substantially chloride-free. The ammonium sulfate by-product of this method has direct use as a fertilizer.

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is a continuation-in-part of provisional application Ser. No. 60/154,860 filed Sep. 20, 1999. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to the production of industrial chemicals. More specifically, the invention describes a novel process for producing chlorine dioxide through the reduction of ammonium chlorate in an aqueous acidic solution. 
     BACKGROUND OF THE INVENTION 
     Until recently, chlorine was used as a bleaching agent in the production of white pulp and paper. However, environmental protection agencies have prohibited the use of chlorine for pulp bleaching since it has been found to produce highly hazardous organochlorine compounds. Chlorine dioxide has replaced chlorine as the primary bleaching agent in the production of white pulp and paper. Chlorine dioxide is also used for water purification. It is now the most important worldwide commodity for these purposes. 
     Existing technologies for commercial production of chlorine dioxide involves the reduction of sodium chlorate/chloric acid with reducing agents such as hydrogen peroxide and glycerol, glycol (See e.g. U.S. Pat. Nos. 5,093,097; 5,091,166; 5,380,517; 5,486,344; and 5,487,881 and Japanese Pat. No. JP88-8203), methanol (U.S. Pat. Nos. 4,978,517 and 5,174,868) and chloride (U.S. Pat. No. 5,458,858; Canadian Pat. Nos. 461586 and 782574). The disclosures of these listed patents are hereby incorporated by reference. These commercial processes incorporate the following chemical reactions: 
     
       
         
               
               
               
             
           
               
                   
               
             
             
               
                 6NaClO 3  + 3H 2 SO 4  + 3H 2 O 2   
                 → 
                 6ClO 2  + 6H 2 O + 3Na 2 SO 4  + 3O 2   
               
               
                 6NaClO 3  + 3H 2 SO 4  + 2CH 3 OH 
                 → 
                 6ClO 2  + 5H 2 O + 3Na 2 SO 4  + O 4  + 
               
               
                   
                   
                 2HCOOH 
               
               
                 NaClO 3  + Alcohols + H 2 SO 4   
                 → 
                 ClO 2  + Na 2 SO 4  + CO 2  + H 2 O 
               
               
                 6HClO 3  + 3H 2 O 2   
                 → 
                 6ClO 2  + 6H 2 O + 3O 2   
               
               
                 6NaClO 3  + 12HCl 
                 → 
                 6ClO 2  + 3Cl 2  + 6H 2 O + NaCl 
               
               
                   
               
             
          
         
       
     
     There are many drawbacks involved with the use of these existing technologies. For instance, methanol is a poisonous and volatile chemical. In addition, as shown above, the major oxidized product formed in methanol reduction processes is formic acid, which is also a toxic chemical. Thus, the use of methanol as a reducing agent in the production of chlorine dioxide creates an environmental hazard. 
     Chloride as a reducing agent is supplied either as hydrogen chloride or as sodium chloride. While chloride is not expensive, its use as a reducing agent in these processes is also disadvantageous since it makes chlorine dioxide with large amounts of chlorine impurity. This is problematic since there has traditionally been no practical means of disposing of chlorine waste material. 
     The use of methanol as a reducing agent in chlorine dioxide processes also has the disadvantage of producing the inevitable by-product sodium sulfate (Na 2 SO 4 ), which is commercially known as salt cake. A part of the salt cake by-product is consumed by pulp mills to make sodium sulfide, a component of black liquor. However, the bulk of the salt cake does not have any use and must simply be disposed of. 
     Hydrogen peroxide can also be used as an efficient reducing agent in the production of chlorine dioxide. Although expensive, the use of hydrogen peroxide is an attractive alternative since it does not result in the formation of the formic acid and chlorine toxic by-products. However, the use of hydrogen peroxide also results in the production of large amounts of undesirable salt cake as a waste product. 
     There is therefore a need in the art for an improved method of producing chlorine dioxide. 
     It is therefore a primary objective of the present invention to provide a method of producing chlorine dioxide which does not form toxic by-products and is environmentally safe. 
     It is a further objective of the present invention to provide a means of producing chlorine dioxide in higher yield with a faster reaction rate than commercially known processes. 
     It is yet a further objective of the present invention to provide a means of producing chlorine dioxide which is economical. 
     It is a further objective of the present invention to provide a means of producing chlorine dioxide without the need for recycling the by-products. 
     These and other objectives will become apparent from the following description. 
     SUMMARY OF THE INVENTION 
     The present invention describes a method of producing chlorine dioxide using a novel chemical reaction. Specifically, the invention involves the chemical reduction of ammonium chlorate in an aqueous acidic solution. The reducing agent may include any one of hydrogen peroxide, sugars, alcohols, aldehydes, ketones, organic acids, sulfur dioxide, ammonium sulfite, ammonium bisulfite, or mixtures thereof. The reduction reaction is performed with or without a catalyst at elevated temperatures. 
     The yield of chlorine dioxide in this invention is over 110% on the basis of reducing agents than in existing processes, as well as at least a 50% higher rate. Further, the resulting chlorine dioxide is substantially free of chlorine impurity. Using sulfuric acid as the acidifying agent, ammonium sulfate is produced as a by-product which may be used as a fertilizer. 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     As set forth above, the present invention discloses the production of chlorine dioxide through the reduction of ammonium chlorate in an aqueous acidic solution, preferably in the absence of a substantial amount of sodium ions, meaning that there are insignificant amounts of sodium ions to produce salt cake by-product. 
     Any source of ammonium chlorate is suitable for this invention. The ammonium chlorate is preferably prepared by the double decomposition reaction of ammonium sulfate and barium chlorate, and most preferably as described in U.S. Pat. No. 5,948,380, the disclosure of which is hereby incorporated by reference. The concentration of chlorate ion (ClO 3   − ) in the aqueous acidic solution is preferably maintained at about 0.5M to saturation, and most preferably between about 1.5M to 4.5M. 
     The source of acidity for this invention may be any strong acid, with sulfuric acid, ammonium bisulfite, chloric acid, perchloric acid, and mixtures thereof being preferred. 
     There are four preferred categories of aqueous acidic solutions for use in the invention. The first category is aqueous solutions of chloric acid or a mixture of chloric acid and ammonium chlorate with acidity ranging preferably from about 0.2N to 7N, and most preferably from about 1.5N to 5N. The chloric acid feed solution is available from the reaction of sulfuric acid with barium chlorate. The preparation of barium chlorate is described in U.S. Pat. No. 5,948,380. 
     The second preferred category of aqueous acidic solutions is aqueous solutions of perchloric acid or a mixture of perchloric acid and chloric acid or a mixture of perchloric acid and chloric acid, with acidity ranging preferably between about 0.2N to 1N, and most preferably between about 1.5N to 5N. The perchloric acid for making such mixtures is available commercially. 
     The third preferred category of aqueous acidic solutions is aqueous solutions of chloric acid and sulfuric acid, with acidity ranging preferably between about 1N to 14N, and most preferably between about 2N to 8N. 
     The fourth preferred category of aqueous acidic solutions is aqueous solutions of sulfuric acid and ammonium bisulfate and ammonium sulfate, with acidity ranging preferably between about 1N to 14N, and most preferably between about 2N to 8N. The source of aqueous acidity in these solution is sulfuric acid and ammonium bisulfate. 
     The concentrated aqueous solution of the reducing agent is fed into a reactor so as to maintain a concentration of reducing agent ranging from about 0.00005M to 0.88M in the reaction mixture. The preferred concentration of reducing agent is from about 0.005M to 0.4M, with the most preferred concentration being maintained in a range of from about 0.01M to 0.2M. 
     The reducing agent used in this invention is not critical, and may include any conventional reducing agents. These may include, but are not limited to hydrogen peroxide, sugars, alcohols, aldehydes, ketones, organic acids, sulfur dioxide, ammonium sulfite, ammonium bisulfite and mixtures thereof. Preferred sugars for use as a reducing agent in this invention are sucrose, glucose and fructose. Preferred alcohols are methanol, glycerol and ethylene glycol. Preferred acids are oxalic acid, malonic acid, citric acid, tartaric acid, and ascorbic acid. The most preferred reducing agents are hydrogen peroxide, glycerol, and sucrose. 
     The reduction of ammonium chlorate to chlorine dioxide by the reducing agents is carried out at a temperature ranging from about 20° C. to 100° C., preferably from about 45° C. to 85° C., and most preferably from about 55° C. to 80° C., and at a pressure ranging from about 50 to 800 mm of Hg, and preferably from about 65 to 500 mm of Hg. 
     Under the above reaction conditions, the reduction of ammonium chlorate in accordance with this invention proceeds smoothly at rates higher than with other industrially used processes using sodium chlorate in the absence of substantial amounts of chloride as a catalyst. As used herein, the phrase “in the absence of substantial amounts of chloride as a catalyst” means there are insufficient amounts of chloride present in the reduction reaction to function as a catalyst. Chloride may, however, be added to the reaction mixture as alkali or earth alkali metal chloride, in particular strontium chloride, hydrochloric acid, or ammonium chloride in an amount ranging from about 0.00001M to 0.6M to accelerate the rate of chlorine dioxide production by these reducing agents. A preferred concentration of chloride catalyst in the reaction is 0.0002M to 0.05M. The addition of ammonium chloride appears to accelerate chlorine dioxide production more than alkali metal chloride, and is therefore the most preferred catalyst. Reduction reactions of this invention may also be catalyzed by transition metal ions, with silver, cobalt, manganese, rare earth metals, or mixtures thereof being preferred. Other appropriate transition metal ions include manganese, cobalt, and strontium. 
     Under similar acidity, chlorate and sulfate concentrations, the rate of chlorine dioxide production in accordance with this invention is over 50% faster in a reaction mixture containing sulfuric acid, ammonium chlorate, and ammonium sulfate than in a mixture containing sulfuric acid, sodium chlorate and sodium sulfate. 
     The chemical combination of ammonium chlorate and the preferred reducing agents of this invention and a preferred aqueous acidic solution of sulfuric acid results in the following net reactions to produce chlorine dioxide, ammonium sulfate, nitrogen, and carbon dioxide: 
     8NH 4 ClO 3 +3H 2 SO 4 +H 2 O 2 →3(NH 4 ) 2 SO 4 +8H 2 O+O 2 +N 2 +8ClO 2    
     33NH 4 ClO 3 +C 12 H 22 O 11 +18H 2 SO 4 →33ClO 2 +32H 2 O+9(NH 4 ) 3 H(SO 4 ) 2 +12CO 2 +3N 2  sucrose 
     17NH 4 ClO 3 +C 3 H 9 O 3 +10H 2 SO 4 →17ClO 2 +16H 2 O+5(NH 4 ) 3 H(SO 4 ) 2 +3CO 2 +N 2  glycerol 
     14NH 4 ClO 3 +C 2 H 6 O 2 +8H 2 SO 4 →14ClO 2 +13H 2 O+4(NH 4 ) 3 H(SO 4 ) 2 +2CO 2 +N 2  ethylene glycol 
     The major by-product, ammonium sulfate, may be used as a fertilizer or recycled by heating in the presence of a catalyst to produce useful industrial chemicals, such as sulfur dioxide and ammonia (U.S. Pat. No. 4,081,515). Thus, unlike the salt cake by-products of existing chlorine dioxide production processes, the ammonium sulfate by-product of the present invention does not require expensive disposal or reprocessing/recycling. 
     As shown above, the present inventors have discovered a way of preventing the production of the unwanted chlorine and sodium sulfate by-product generated by chlorine dioxide plants. This finding could potentially save the chemical industry large sums of money which would have otherwise been spent disposing of this waste product. 
     In addition, the methods of this invention using ammonium chlorate produces chlorine dioxide in a yield of 110% on the basis of reducing agent, and at a greater than 50% higher rate than in conventional processes using sodium chlorate, as demonstrated in Examples 2, 4, and 9 below. 
    
    
     The following examples are offered to illustrate but not limit the invention. Thus, they are presented with the understanding that various formulation modifications as well as reactor modifications may be made and still be within the spirit of the invention. 
     EXAMPLE 1 
     Preferred Method of Production of Chlorine Dioxide Using Hydrogen Peroxide as a Reducing Agent 
     An aqueous solution of 304 g/h NH 3 ClO 3  together with 150 g/h H202 of 30% solution was continuously added to a laboratory chlorine dioxide generator. H 2 SO 4  of 50% concentration was added in order to keep the acid strength of 4.56N. An aqueous solution of 4.0 g NH 4 Cl was also added together with an excess of chlorate solution. The generator was run continuously at a temperature of around 70° C., and chlorine dioxide was collected under reduced pressure of 400 mm of Hg to keep the reaction mixture at boiling during the chlorine dioxide collection. A neutral salt (NH 4 ) 2 SO 4  was crystallized in the crystallization region. The rate of chlorine dioxide production was 7.78 kg/l/d, with a yield of 99% and a rate of production of 8007×10 −5  moles/min/l reaction-mix. 
     EXAMPLE 2 
     Preferred Method of Production of Chlorine Dioxide Using Hydrogen Peroxide as a Reducing Agent in Acidic Solution Saturated with Ammonium Sulfate 
     A mixture of 171 g/h NH 4 ClO 3  and 51 g/h, H 2 O 2  (30%) together with 3.6 g/h NaCl was continuously added to a chlorine production generator. H 2 SO 4  was also fed to the reaction mixture to keep the acid strength of 4.0 N. The reaction mixture was saturated with (NH 4 ) 2 SO 4 . The generator was run continuously at temperature around 80° C., and chlorine dioxide was collected under reduced pressure of 250 mm of Hg in order to keep the reaction mixture at boiling during collection of ClO 2 . A neutral salt (NH 4 ) 2 SO 4  was crystallized in the crystallization region. Production of chlorine dioxide was 4.66 kg/l/d, and the yield was 99% with a rate of chlorine dioxide production of 4800×10 −5  moles/min/l reaction-mix. 
     This experiment was conducted in accordance with Example 3 of U.S. Pat. No. 5,091,166 to Engström, only substituting ammonium chlorate for the sodium chlorate. While Engström&#39;s rate of chlorine dioxide production was only 1.5 kg/l/day, as shown above, Applicant was able to achieve a rate of 5.25 kg/l/day, or a rate 3.1 times higher than that of Engström. 
     EXAMPLE 3 
     Preferred Method of Production of Chlorine Dioxide Using Hydrogen Peroxide as a Reducing Agent 
     An aqueous solution of 134 g/h NH 4 ClO 3  together with 60 g/h H 2 O 2  (30% solution) was continuously added to a laboratory chlorine dioxide production generator. A required amount of H 2 SO 4  was also fed to the reaction mixture to keep the acid strength of 4.0 N. An aqueous solution of 1.96 g/h NaCl was added together with excess NH 4 ClO 3  solution. The generator was run continuously at temperature around 70° C., and chlorine dioxide was collected under reduced pressure of 150 mm of Hg in order to keep the reaction mixture at boiling during collection of ClO 2 . A neutral salt (NH 4 ) 2 SO 4  was crystallized in the crystallization region. Production of chlorine dioxide was 3.62 kg/l/d, and the yield was 95% with a rate of chlorine dioxide production of 3628×10 −5  moles/min/l reaction-mix. 
     EXAMPLE 4 
     Preferred Method of Production of Chlorine Dioxide Using Hydrogen Peroxide as a Reducing Agent 
     A mixture of 172 g/h NH 4 ClO 3  together with 77 g/h H 2 O 2  (30% solution) was continuously added to a laboratory chlorine dioxide production generator. A required amount of H 2 SO 4  was also fed to the reaction mixture to keep the acid strength of 4.0 N. An aqueous solution excess of NH 4 ClO 3  together with 3.25 g/h NaCl was added to the generator. The reaction mixture in the generator was kept at boiling throughout the collection of ClO 2 , and chlorine dioxide was collected at 70° C. under reduced pressure of 150 mm of Hg. A neutral salt (NH 4 ) 2 SO 4  was crystallized in the crystallization region. Production of chlorine dioxide was 4.10 kg/l/d, and the yield was 98% with a rate of chlorine dioxide production of 4218×10 −5  moles/min/l reaction-mix. 
     This experiment was conducted in accordance with Example 1 of U.S. Pat. No. 5,091,166 to Engström, only substituting ammonium chlorate for the sodium chlorate. While Engström&#39;s rate of chlorine dioxide production was only 1.2 kg/l/day, as shown above, Applicant was able to achieve a rate of 4.10 kg/l/day, or a rate 3.4 times higher than that of Engström. 
     EXAMPLE 5 
     Preferred Method of Production of Chlorine Dioxide Using Hydrogen Peroxide as a Reducing Agent in Acidic Solution Saturated with Amimonium Sulfate 
     A mixture of 173 g/h NH 4 ClO 3  together with 51 g/h H 2 O 2  (30% solution) was continuously added to a laboratory chlorine dioxide production generator. A required amount of H 2 SO 4  was also fed to the reaction mixture to keep the acid strength of 4.0 N. An aqueous solution excess of NH 4 ClO 3  together with 3.2 g/h NH 4 Cl was added to the generator. The reaction mixture was saturated with (NH 4 ) 2 SO 4 . The generator was continuous run at a temperature of around 80° C. Chlorine dioxide was collected under reduced pressure of 250 mm of Hg while keeping the reaction mixture at boiling. A neutral salt (NH 4 ) 2 SO 4  was crystallized in the crystallization region. Production of chlorine dioxide was 5.25 kg/l/d, and the yield was 99% with a rate of chlorine dioxide production of 5400×10 −5  moles/min/l reaction-mix. 
     EXAMPLE 6 
     Preferred Method of Production of Chlorine Dioxide Using Sugar as a Reducing Agent 
     A water solution of 225 g/h NH 4 ClO 3  together with 60 g/h sugar (50% aqueous solution) were added continuously to a laboratory reactor. A required amount of H 2 SO 4  (50% solution) was also added to keep the acidity 7N. The reactor was run continuously at temperature around 65° C., and chlorine dioxide was collected under reduced pressure 250 mm of Hg in order to keep the reaction mixture boiling during the collection of chlorine dioxide. The crystals of (NH 4 ) 3 H(SO 4 ) 2  were isolated in the crystal region. The chlorine dioxide production was 4.70 kg/l/d, and yield was 95% with a rate of production of 4837×10 −5  moles/min/l reaction mix. 
     EXAMPLE 7 
     Preferred Method of Production of Chlorine Dioxide Using Sugar as a Reducing Agent 
     7A—NH 1 ClO 3 /Sugar System 
     To a chlorine dioxide production generator, a aqueous solution of 255 g/h NH 4 ClO 3  and 60 g/h sugar (50% aqueous solution) were added continuously. A 50% solution of H 2 SO 4  was also added to keep the aqueous acidity at 8N. The generator was run continuously at a temperature of around 70° C. while chlorine dioxide was collected under reduced pressure of 250 mm of Hg. Reduced pressure was maintained in order to keep the reaction mixture at boiling. The crystals of (NH 4 ) 3 H(SO 4 ) 2  were isolated in the crystal region. The chlorine dioxide production was 12.50 kg/l/d, and the yield was 99% with a rate of production 12869×10 −5  moles/min/l reaction mix. 
     7B—NaClO 3 /Sugar System 
     319 g/h NaClO 3  and 60 g/h sugar (50% solution) was added to a chlorine dioxide production generator. A required amount of H 2 SO 4  was also added to keep acid at 8.0N. The generator was continuously run at 70° C., and chlorine dioxide was continuously collected under reduced pressure of 250 mm of Hg. The production of chlorine dioxide was 7.78 kg/l/d and at a rate of 8000×10 −5  moles/l/min. 
     Thus, as shown above, the production of chlorine dioxide was much more efficient using Applicant&#39;s method using ammonium chlorate than the previous method using sodium chlorate. 
     EXAMPLE 8 
     Preferred Method of Production of Chlorine Dioxide Using Sugar as a Reducing Agent 
     A water solution of 170 g/h NH 4 ClO 3  and 50 g/h sugar (50% aqueous solution) were continuously added to a chlorine production generator at temperature around 80° C. 50% aqueous H 2 SO 4  was added to keep the acid concentration at 8N. The generator was run continuously at a temperature of around 80° C. during which time chlorine dioxide was collected under reduced pressure of 150 mm of Hg. The crystals of (NH 4 ) 3 H(So 4 ) 2  were isolated in the crystal region. The chlorine dioxide production was 24.50 kg/l/d, and the yield was 99% with a production rate of 25185×10 −5  moles/min/l reaction mix. 
     EXAMPLE 9 
     Preferred Method of Production of Chlorine Dioxide Using Glycerol as a Reducing Agent 
     255 g/h NH 4 ClO 3  aqueous solution and 30 g/h glycerol (50% aqueous solution) were added continuously to a laboratory chlorine dioxide generator. A H 2 SO 4 /50% aqueous solution was also added to maintain the acidity of the reaction mixture at 7N. The reactor was run continuously at around 70° C. while chlorine dioxide was collected under reduced pressure at 250 mm of Hg. The crystals of (NH 4 ) 3 H(SO 4 ) 2  were isolated in the crystal region. The chlorine dioxide production was 8.60 kg/l/d, and the yield was 99% with a rate of production 8848×10 −5  moles/min/l reaction mix. 
     This experiment was conducted in accordance with Example 3 of U.S. Pat. No. 5,093,097 to Engström, only substituting ammonium chlorate for the sodium chlorate. While Engström&#39;s rate of chlorine dioxide production was only 1.7 kg/l/day, as shown above, Applicant was able to achieve a rate of 8.60 kg/l/day, or a rate over 5 times hither than that of Engström. 
     EXAMPLE 10 
     Preferred Method of Production of Chlorine Dioxide Using Ethylene Glycol as a Reducing Agent 
     To a laboratory chlorine dioxide generator an aqueous solution of 170 g/h NH4 ClO 3  and 30 g/h ethylene glycol (20% aqueous solution) were added continuously. 50% aqueous H 2 SO 4  solution was added to keep the acidity at 7N. The generator was run continuously at around 65° C. during which time chlorine dioxide was collected at a reduced pressure 350 mm of Hg. Reduced pressure was applied to keep the reaction mixture at boiling. The crystals of (NH 4 ) 3 H(SO 4 ) 2  were isolated in the crystal region. The chlorine dioxide production was 8.75 kg/l/d, and the yield 99% with a rate of production 8992×10 −5  moles/min/l reaction mix. 
     EXAMPLE 11 
     Determination of Rates of Chlorine Dioxide Production in Flow Reactor 
     The rate determination experiments were carried out as described in Examples 1-5. The rates were calculated based on the amount of chlorine dioxide collected, time of collection and the volume of the reaction mixtures. The rates and reaction conditions are given in Table 1 below: 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Results of Flow Reactor Experiments from Hydrogen Peroxide Reduction 
               
             
          
           
               
                   
                 Amount 
                 Pressure 
                   
                   
                   
                   
                   
                   
               
               
                 Example 
                 of ClO 2   
                 in mm 
                   
                 Catalyst 
                 Temp., 
                 Molarity of 
                 Normality 
                 ClO 2  rate 
               
               
                 Numbers 
                 in g/l/min 
                 of Hg 
                 Catalyst 
                 Molarity 
                 ° C. 
                 Chlorate ion 
                 of H 2 SO 4   
                 moles/min./lit. 
               
               
                   
               
               
                 1 
                 7.78 
                 400 
                 NH 4 Cl 
                 0.0010  
                 70 
                 2.00 
                 4.56 
                 8007 × 10 −5   
               
               
                 2 
                 4.66 
                 250 
                 NaCl 
                 0.00045 
                 80 
                 2.00 
                 4.00 
                 4800 × 10 −5   
               
               
                 3 
                 3.62 
                 150 
                 NaCl 
                 0.00136 
                 70 
                 2.00 
                 4.00 
                 3628 × 10 −5   
               
               
                 4 
                 4.10 
                 150 
                 NH 4 Cl 
                 0.00056 
                 70 
                 2.00 
                 4.00 
                 4218 × 10 −5   
               
               
                 5 
                 5.25 
                 250 
                 NH 4 Cl 
                 0.00049 
                 80 
                 2.00 
                 4.00 
                 5400 × 10 −5   
               
               
                   
               
             
          
         
       
     
     Examples 2 and 5 were carried out in a reaction mixture saturated with ammonium sulfate. 
     EXAMPLE 12 
     Determination of Rates of Chlorine Dioxide Production in Flow Reactor 
     The rate determination experiments were carried out as described in Examples 6-10. The rates were calculated based on the amount of chlorine dioxide collected, time of collection and the volume of the reaction mixtures. The rates and reaction conditions are given in Table 2 below: 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Results of Flow Reactor Experiments from Sugar, Glycerol and Ethylene Glycol 
               
             
          
           
               
                   
                 Amount 
                   
                   
                 Molarity of 
                   
                   
                   
               
               
                 Reducing 
                 of ClO 2   
                 Pressure in 
                 Temp., 
                 reducing 
                 Molarity of 
                 Normality 
                 ClO 2  rate 
               
               
                 Agents 
                 in g/l/min 
                 mm of Hg 
                 ° C. 
                 agents 
                 NH 4 ClO 3   
                 of H 2 SO 4   
                 moles/min./lit. 
               
               
                   
               
             
          
           
               
                 Sugar 
                 4.70 
                 250 
                 65 
                 0.058 
                 2.0 
                 7 
                  4837 × 10 −5   
               
               
                   
                 12.50 
                 250 
                 70 
                 0.058 
                 2.0 
                 8 
                 12869 × 10 −5   
               
               
                   
                 24.50 
                 150 
                 80 
                 0.073 
                 2.0 
                 8 
                 25185 × 10 −5   
               
               
                 Glycerol 
                 8.60 
                 250 
                 70 
                 0.197 
                 2.0 
                 7 
                  8848 × 10 −5   
               
               
                 Ethylene 
                 8.75 
                 350 
                 65 
                 0.322 
                 2.0 
                 7 
                  8992 × 10 −5   
               
               
                 Glycol 
               
               
                   
               
             
          
         
       
     
     It is therefore submitted that the present invention accomplishes at least all of its stated objectives.