Patent Publication Number: US-5296422-A

Title: Molybdenum trioxide bonded basic monolith and method

Description:
This application is a continuation of application Ser. No. 07/714,474 filed on Jun. 13, 1991, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     This invention relates to basic refractory monoliths and, more particularly, it concerns a molybdenum trioxide bonded basic refractory and method. 
     Basic monoliths are refractory compositions which are either preformed or formed on site. They are installed by various forming techniques, such as casting, fettling, gunning, spraying, troweling, or in some cases by pressing. The term &#34;basic&#34; implies that the major component in the mix is a base oxide, such as lime, magnesia, or a combination of these common refractory oxides. 
     In the past, chromic acid (CrO 3 ) has been the preferred binder for basic monoliths. Use of this binder imparted monolithic shapes with exceptional strength and slag resistance. Chromic acid contains the element chromium in the +6 valence state which is commonly referred to as hexavalent chrome. 
     While use of the chromic acid binder has provided adequate utility, recently, there has been a great deal of concern over the use of chromic acid because chromium +6 may be toxic and carcinogenic. For example, the EPA has forbidden routine disposal of materials containing more than 5 ppm of soluble chromium. 
     The refractory industry, in response to EPA concerns, has abandoned the use of chromic acid as a binder and has used as substitutes epsom (MgO·SO 4  ·7H 2  O) salts, phosphates, silicates, nitre cake (NaH·SO 4  ·H 2  O), sulfamic acid (H SO 3  ·NH 2 ), citric acid, and anhydrous boric acid (H 3  ·BO 3 ) either individually or in combination. Although these substitute binders have provided adequate service, they have not provided equivalent service to that achieved using chromic acid. 
     In light of the foregoing, there is a need for an improved basic refractory monolith including a binder which provides desired levels of slag resistance and strength and is environmentally safe. 
     SUMMARY OF THE INVENTION 
     In accordance with the present invention, the problems associated with the use of chromic acid (CrO 3 ) binders are substantially overcome by a basic refractory monolith incorporating molybdenum trioxide (MoO 3 ) as the binding agent. 
     It has been unexpectedly discovered that molybdenum trioxide (also referred to as molybdic oxide) is an effective substitute for chromic acid in basic monoliths. Molybdic oxide (MoO 3 ) is non-toxic, non-carcinogenic, and, as such, provides a refractory which is safe to handle and dispose of. 
     Also, it was found that small additions of MoO 3  and a base, such as sodium hydroxide or sodium carbonate, to deadburned magnesite mixes allowed the mixes to develop a set at room temperature within an hour. Such a property is desired as these mixes are often installed between forms, the forms stripped soon after, and then heat is applied to sinter the monolith. Simple drying of the monolith to temperatures of 250° F. resulted in a dramatic increase of strength. A strong basic organic pH modifier such as triethylamine may also be used. 
     Additionally, molybdic oxide is only partially soluble in water. This is an important feature since there is less tendency for the molybdic oxide to migrate during drying of the shape. Conventional silicate and phosphate binders tend to be readily soluble in water. Hence, during drying of conventional monoliths, a gradient develops through the shape leaving a weak interior and a stronger exterior. Such a gradient is unacceptable in many applications. 
     Accordingly, a principal object of the present invention is to provide a basic refractory monolith having a molybdenum trioxide binder. Another and more specific object of the invention is the provision of a binder for basic monoliths which imparts the desired levels of strength, is environmentally safe, provides a set at room temperature within a desired time span, and provides the monolith with slag resistance comparable to chromic acid bonded shapes. Other objects and further scope of applicability of the present invention will become apparent from the detailed description to follow taken in conjunction with the accompanying tables. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     In accordance with the present invention, the problems associated with the use of chromic acid (CrO 3 ) binders are addressed by a basic refractory monolith incorporating molybdenum trioxide (molybdic oxide, MoO 3 ) as the binding agent. The aggregate used to make the monolith may be deadburned magnesite, calcined dolomite, magnesium aluminate spinel, chrome ore and combinations thereof. It is to be understood that the refractory monolith of the present invention is suited for refractory applications including mortars, shapes, grouts, plastics, castables, dry mixes, and wet mixes. 
     Molybdic oxide (MoO 3 ) is less soluble than chromic acid in water. It appears that the solubility or at least reactivity of MoO 3  can be maximized by the addition of a high pH solute to the water. Experiments showed that ground sodium hydroxide additions to a deadburned magnesite mix which contained small additions of MoO 3  resulted in an initial set at room temperature within an hour (Table I). Other bases provided similar results, but require more time to develop a set. Additions of boric acid and citric acid seemed to retard the air set. Reagent grade sodium carbonate was found to be effective although it is assumed that common soda ash would probably have the same effect as a pH modifier. 
     
                       TABLE I                                                     
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       100% Deadburned Magnesite Fines                                    
       Plus additions:                                                    
        2% Molybdic Trioxide                                              
        1% Sodium Hydroxide                                               
       25% Water                                                          
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     Above mixture develops an air set within one hour. 
     Initial development of molybdic oxide containing mixes is shown in Table II. Mixes A to E involve a study of various grinds and two levels of sodium carbonate either with and without a starch addition to the mix. Mix C, a fine grind mix with a lower level of sodium carbonate, was the best gunning mix of the series. Mix C had a low water requirement, formed a firm panel when gunned, and only had moderate rebounds. 
     
                                           TABLE II                                
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Mix Development                                                           
Mix:               A   B    C    D   E   Comparative Data                 
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Deadburned Magnesite, 4/10 mesh                                           
                    28%                                                   
                       15%  15%   28%                                     
                                      15%                                 
                                         Deadburned                       
                                                 Deadburned               
                                                        Deadburned        
Deadburned Magnesite, 10/28 mesh                                          
                    48 50   50    48  50 Magnesite                        
                                                 Magnesite                
                                                        Magnesite         
Deadburned Magnesite, -28 mesh                                            
                    11 24   24    11  24 Gunning Mix                      
                                                 Gunning                  
                                                        Gunning Mix       
Deadburned Magnesite, Fines                                               
                    7   5    5.5   7   5.5                                
                                         W/Epsom Salt                     
                                                 w/Chromic                
                                                        w/Chromic         
(55% -325 mesh)                          Bond    Acid Bond                
                                                        Acid Bond         
Crude Clay          3   3    3     3   3         Brand A                  
                                                        Brand B           
Molybodic Oxide     2   2    2     2   2                                  
Sodium Carbonate    1   1    0.5   1   0.5                                
Plus Additions     --  --   --     0.5                                    
                                       0.5                                
Starch                                                                    
Moisture Required to Achieve a                                            
                    9.4                                                   
                        8.3  6.8   6.8                                    
                                      10.4                                
                                          12.7    6.0    6.5              
Gunning Consistency, %                                                    
Gunning Characteristics:                                                  
                   OK  Better                                             
                            Better                                        
                                 Not As                                   
                                     OK  Poor    Poor   OK                
                       Than A                                             
                            Than A                                        
                                 Good                                     
                            Or B as C                                     
Properties of Gunned Panels                                               
Bulk Density, pcf - After Drying at                                       
                   163 --   --    154                                     
                                      153                                 
                                          156     163    170              
250° F.:                                                           
After 3000° F. Reheat:                                             
                   155 --   --    145                                     
                                      150                                 
                                         --      --     --                
Modulus of Rupture, psi                                                   
After Drying at 250° F.:                                           
                   --  --   --    860                                     
                                      960                                 
                                          600    1290    950              
After 3000° F. Reheat:                                             
                   510 --   --    460                                     
                                      620                                 
                                         --      --     --                
At 2500° F.:                                                       
                    10 --   --   --  --  --      --     --                
Cold Crushing Strength, psi                                               
After Drying at 250° F.:                                           
                   --  --   --   2870                                     
                                     4200                                 
                                         4550    6440   5110              
After 3000° F. Reheat:                                             
                   400 --   --    650                                     
                                      910                                 
                                         --      --     --                
3000° F. Reheat                                                    
% Linear Change:   +0.3                                                   
                       --   --    +0.5                                    
                                      -0.2                                
                                         --      --     --                
% Volume Change:   -0.4                                                   
                       --   --    -1.1                                    
                                      -3.3                                
                                         --      --     --                
Desired Screen Analysis                                                   
  4 on 10 mesh      25 14   --   --  --  --      --     --                
  10 on 28 mesh     45 45   --   --  --  --      --     --                
  28 on 65 mesh     10 16   --   --  --  --      --     --                
 -65                20 25   --   --  --  --      --     --                
-325               10-15                                                  
                       10-15                                              
                            --   --  --  --      --     --                
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     A commercially available molybdic oxide that is useful in the practice of the present invention is a Noranda molybdic oxide product sized -20 mesh with a typical screen analysis of: 
     Company: Noranda 
     Product: Molybdic Oxide 
     
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Typical Screen                                                            
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       +20 M     3-5                                                      
       -20 + 48 M                                                         
                 10-15                                                    
       -48 + 65 M                                                         
                 3-5                                                      
       -65 + 100 M                                                        
                 3-5                                                      
       -100 + 200 M                                                       
                 18-20                                                    
       -200 + 325 M                                                       
                 15-25                                                    
       -325      30-35                                                    
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     A preferred embodiment of the invention provides a basic refractory mix consisting essentially of up to 5 wt %, preferably about 0.5 wt %, pH modifier, up to 10 wt %, preferably about 2 wt % molybdic oxide, up to 10 wt %, preferably about 3 wt % crude clay, and 75 to 99 wt % basic aggregate. Preferably, the size of the molybdic oxide particles is -20 mesh (smaller than -20 mesh), preferably -325 mesh. 
     Thus it will be appreciated that, as a result of the present invention, a highly effective basic monolith with an effective slag-resistant bond is provided by which the principal object and others are completely fulfilled. It is contemplated and will be apparent to those skilled in the art from the foregoing description and accompanying tables that-variations and/or modifications of the disclosed embodiment may be made without departure from the invention. Accordingly, it is expressly intended that the foregoing description and accompanying tables are illustrative of a preferred embodiment only, not limiting, and that the true spirit and scope of the present invention be determined by reference to the appended claims.