Patent Publication Number: US-4734258-A

Title: Morpholinohexose reductone as an oxygen scavenger

Description:
Dissolved oxygen in water is undesirable when such waters are used in industrial applications. Oxygen containing waters cause corrosion in such industrial equipment as boilers, heat exchangers, and oil well equipment. 
     A common method of combating this problem is to scavenge oxygen with chemicals. The invention deals with an improved chemical for scavenging oxygen that is efficient and is organic and readily available. 
    
    
     FIGS. 1-3 illustrate the structure of some disclosed organic compounds. 
    
    
     THE INVENTION 
     In accordance with the invention, it has been found that oxygen may be scavenged from industrial waters by using from about between 1 to 1,000 ppb by weight in the water of 2,5-dihydroxy-5-methyl-3-(4-morpholinyl)-2-cyclopenten-2-one, also known as morpholinohexose reductone. This material is illustrated as FIG. 1. A preferred dosage is 20-500 ppb in a typical industrial water system or about 2 parts to 50 parts of morpholinohexose reductone per part of oxygen by weight. 
     TEST METHOD 
     Initial kinetic studies of scavengers with dissolved oxygen were carried out at 32° C.±0.1° in air-saturated 0.025M NaHCO 3  containing about 2.5×10 -4  M oxygen. These reactions were carried out in a 500-ml round bottom flask equipped with a pH electrode, an Orion Model 97-08 oxygen electrode, thermometer and a septum-covered port for injection for scavenger and catalyst solutions and immersed in a thermostated water bath. The reaction was stirred continuously with a 1-inch Teflon-coated magnetic bar. After injection of scavenger and catalyst, the disappearance of oxygen was followed with the Orion electrode signal. 
     High-temperature measurements of effectiveness were carried out by passing a dilute, aerated solution of scavenger at 40 ml/min through a 20 ft. by 1/4 inch copper coil heated to 190° F. Concentrations of oxygen are measured before and after the coil with Orion Model 97-08 electrodes. 
     EVALUATION OF THE INVENTION 
     Using the above test method, the results using morpholinohexose reductone in comparison with other known or proposed oxygen scavengers is presented below in Table I. The comparison with isoascorbic acid, a well-known industrial scavenger, is particularly illustrative in demonstrating the efficacy of the invention. Two additional condensation products of hexose and amines are illustrated in FIGS. 2 and 3 and are included in Table II. Neither material reacts with dissolved oxygen at a detectable rate. 
     
                       TABLE I                                                     
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Oxygen Scavenging Tests at 32° C. ± 0.1°                 
Examples of Typical Results.sup.a                                         
              Conc.    [cu(II)]     Initial Rate                          
Scavenger     M × 10.sup.4                                          
                       × 10.sup.4,b                                 
                               pH   M/s × 10.sup.7,c                
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Morpholinohexose                                                          
              5.5      0       9.6  2.2                                   
reductone                                                                 
Morpholinohexose                                                          
              5.5      0.16    9.6  40.5                                  
reductone                                                                 
Diethanolaminohexose                                                      
              5.7      0       9.4  0                                     
morpholinohexose                                                          
              5.6      0.16    9.4  0                                     
isoascorbic acid                                                          
              5.6      0       9.6  1.1                                   
dihydroxyacetone                                                          
              3.77     0.16    10.1 0.66                                  
dihydroxyacetone                                                          
              16.7     0       9.3  0                                     
dihydroxyacetone                                                          
              16.7     0.16    9.3  0.62                                  
fructose      8.3      0       10.0 0.66                                  
fructose      8.3      0.16    10.0 0.66                                  
hydroxylamine 3.6      0.24    9.35 13.0                                  
hydroxylamine 15.0     0       9.35 0.01                                  
aminoguanidine                                                            
              11.0     0       10.0 0.10                                  
aminoguanidine                                                            
              11.0     0.16    10.0 2.3                                   
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 Notes:                                                                   
 .sup.a Kinetic runs in airsaturated 0.025M NaHCO.sub.3 adjusted to pH wit
 NaOH;                                                                    
 .sup.b as CuSO.sub.4 ;                                                   
 .sup.c Initial rate = -d[O.sub.2 ]/dt at time = O; as comparison 1 ppm/mi
 = 5.2 × 10.sup.-7 M/s.                                             
 
    
     
                       TABLE II                                                    
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High Temperature (˜88° C.) Testing of Various Oxygen         
Scavengers Oxygen reduced (as %) at various mole ratios                   
of reactants ([scavenger].sub.o :[O.sub.2 ].sub.o).sup.a,b                
Scavengers                                                                
          1       1.5   2    2.5  4    5    8    10                       
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Morpholinohex-                                                            
           47%    --    79%  --   86%  --   88%  --                       
ose reductone                                                             
(I)                                                                       
Dihydroxyace-                                                             
          0       --    --   15%  --   81%  --   --                       
tone                                                                      
Aminoquanidine                                                            
          42      35    54   --   46   --   58   --                       
(Acetate)                                                                 
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 NOTES:                                                                   
 .sup.a % reduction after 11 minutes of continuous steady flow            
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