Methods and compositions for reclaiming concrete
This is a continuation of application Ser. No. 08/006,017 filed on Jan. 15, 1993, now abandoned, which in turn is a continuation of application Ser. No. 07/936,694 filed on Aug. 27, 1992, now abandoned, which in turn is a continuation of application Ser. No. 07/790,949 filed on Nov. 12, 1991, now abandoned, which in turn is a continuation of application Ser. No. 07/572,512 filed on Aug. 24, 1990, now abandoned, which in turn is a division of application Ser. No. 07/494,876 filed on Mar. 8, 1990, now U.S. Pat. No. 4,964,917, which in turn is a continuation of application Ser. No. 07/088,180 filed on Aug. 21, 1987, now abandoned, which in turn is a continuation of application Ser. No. 06/900,489 filed on Aug. 26, 1986, and now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     This invention relates to concrete reclaimation. In one particular aspect it relates to methods and compositions for reclaiming concrete which is normally discarded. 
     It is presently the practice in the concrete industry that when a ready-mix truck returns from a job with an unused portion of concrete, this excess concrete is dumped into a disposal site. This practice is both economically and environmentally undesirable. 
     The present invention provides methods and admixture compositions to reclaim this wasted concrete. 
     THE INVENTION 
     Broadly, the concrete reclaiming method of this invention comprises the steps of: 
     1--retarding the hydration of the unused portion of concrete returned from a job site by adding within 0.5 to 7 hours, preferably 1 to 4 hours a retarding agent which is a chelating agent for calcium, e.g., [nitrilotris (methylene)]tris, phosphonic acid to the concrete, to retard hydration for normally an additional 12 to 90 hours, preferably 12 to 72 hours; 
     2--optionally, at the end of the desired retardation period, diluting the retarded concrete with fresh concrete; and 
     3--adding hydration accelerating agents (e.g., ASTM C494 Type C admixture) to the concrete to restore it to a settable state. Optionally, water reducing strength enhancers (e.g., ASTM C494 Type A admixture) may be added with the accelerating agents. 
     It will be appreciated by those skilled in the art that the following factors will influence (a) the retardation time and retarder concentration, and (b) the acceleration time and accelerator and water reducing strength enhancer concentration. 
     --The ASTM type of cement. While Types I-IV are applicable to the present process, Types I and II are preferred. The amount of accelerator to be added to the cement (step 3 above) may be dependent on the degree of fly ash substitution in the cement. In general, more accelerator is necessary with fly ash substitution. 
     --Time of addition of the retarding agent to cement. Usually concrete is placed within 1.5 hours of mixing, and the retarding agent would be added at the end of the placing period. However, the actual time of adding the retarding agent may be prolonged if the concrete maintains the required slump, air content, and unit weight. It is preferred that the retarding agent be added to the cement within about 1 to 4 hours after initial mixing. 
     --Time of set. The set rate of concrete may be affected by the temperature, e.g., the higher the temperature, the faster the set rate; and also by the concentration of the retarder and accelerator and their ratio to each other. In addition the amount of the water reducing strength enhancer may also have an effect on the concentration of retarder to accelerator. Additionally the set rate is also dependent on the volume of concrete to be treated. The volume of concrete effects the temperature of the concrete. A larger volume of concrete will set up sooner than a smaller volume because of the greater amount of heat liberated. A preferred temperature range is from 32° F. to 110° F., preferably 32° F. to 99° F. At a temperature of from 32° F. to 69° F. a preferred time of addition of the retarding agent is from about 1 to 4 hours. At a temperature of from 70° F. to 99° F. a preferred time of addition of the retarding agent is from about 1 to 3 hours. 
     --Percent of old (reclaimed) concrete to fresh concrete in the final mix. The old concrete may range from about 5% to 100% with the fresh concrete from 95% to 0%. Preferably the old concrete may be from about 10% to 30%, and the fresh concrete from about 90% to 70% of the concrete mixture. Clearly, the higher the proportion of reclaimed concrete, the more accelerator must be added. 
     --The amounts of added retarding agent and accelerating agent may vary depending upon the types and amounts of the admixtures in the original cement and the freshly added cement. 
    
    
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     The retarders used in the process of the invention must, when used in .appropriate quantities, be long-acting and reversible in action, so that addition of an accelerator can restore the concrete to essentially its original state. 
     The preferred retarders are phosphonic acid derivatives, more preferably those containing hydroxy and amino groups, which are capable of acting as calcium chelating agents. Particularly preferred retarders of this type are compounds of DEQUEST (R.T.M.) series, sold by Monsanto Co. (St. Louis, Mo.), in particular: DEQUEST 2000 Phosphonic acid, [nitrilotris (methylene)]tris. DEQUEST 2006 Phosphonic acid, [nitrilotris (methylene)]tris-, pentosodium salt., DEQUEST 2010 Phosphonic acid, (1, hydroxyethylidene) bis. DEQUEST 2016 Phosphonic acid, (1,hydroxyethylidene) bis-, tetrasodium salt. DEQUEST 2041 Phosphonic acid, [1,2-ethanediylbis [nitrilobis (methylene)]]tetrakis. DEQUEST 2047 Phosphonic acid, [1,2-ethanediylbis [nitrilobis (methylene)]]tetrakis-, calcium sodium salt (2:5:6). DEQUEST 2051 Phosphonic acid, [1,6-hexanediylbis [nitrilobis (methylene)]]tetrakis. DEQUEST 2054 Phosphonic acid, [1,6-hexanediylbis [nitrilobis (methylene)]]tetrakis-, potassium salt. DEQUEST 2060 Phosphinic acid, [[bis[2-bis (phosphonomethyl) amino]ethyl]amino]methyl]. DEQUEST 2066 Phosphonic acid, [[(phosphonomethyl) imino] bis [(2,1-ethanediylnitrilo) tetrakis (methylene)]] tetrakis-, sodium salt. 
     Other suitable retarders include hydroxycarboxylic acids and their salts, including citric, gluconic, tartaric, and glucoheptanoic acids; polycarboxylic acids and their salts, e.g., polymaleic, polyfumaric, polyacrylic and polymethacrylic acids, preferably of low molecular weight; fumaric, itaconic and malonic acids and their salts; antioxidants e.g., ascorbic acid, isoascorbic acid; polymers e.g., sulphonic acid--acrylic acid copolymers, polyhydroxysilanes and polyacrylamide, preferably of low molecular weight; carbohydrates, e.g., sucrose and corn syrup; and lignosulphonates, e.g., calcium lignosulphonates. Of these, the hydroxycarboxylic acids, polycarboxylic acids, ascorbic acid, isoascorbic acid, carbohydrates and polyhydroxysilanes are preferred. 
     More preferred retarders are mixtures of at least one retarder of the phosphonic acid type with at least one retarder of a different type. As many of the non-phosphonic acid retarders e.g., citric acid also have water-reducing properties, these may also have the effect of increasing the compressive strength of the final set concrete. 
     Particularly preferred retarders are mixtures of the DEQUEST series with citric acid, particularly DEQUEST 2000/citric acid. Preferred ratios of DEQUEST to citric acid are from 1:1 to 2:1. 
     A preferred retarding formulation (R) of this invention is: 
     0.318% of phosphonic acid, [nitrilotris (methylene)]tris-DEQUEST 2000 
     0.2000% of citric acid 
     The percentages are lb per 1000 lbs. of cement at 100% active material, which may be added for example as 40 oz. of solution to 100 lbs. of cement. 
     Preferred accelerating agents which may be used in this invention to reactivate the retarded concrete are those classified in ASTM C 494 Type C admixtures. Preferred accelerator compositions are chloride-free and may contain for example calcium salts e.g., calcium nitrate and calcium formate, thiocyanates, triethanolamine and glycolurils e.g., trimethylolglycoluril. A particularly preferred accelerator of this type is that sold by Master Builders Inc. (Cleveland, Ohio) under the trademark POZZOLITH 555 A. 
     Preferred water-reducing strength enhancers which may optionally be added together with the accelerating agent are those classified in ASTM C 494 as Type A admixtures; that is they are water reducing agents which of themselves have no substantial retarding or accelerating effect. A particularly preferred material is that sold by Master Builders Inc. under the trademark POZZOLITH POLYHEED. 
     It is also possible, instead of using a combination of Type C admixture as accelerator and a Type A admixture as water-reducing agent, to use a single addition of a Type E admixture, which is water-reducing accelerator. The combination of a Type C and a Type A product is however preferred. 
     In the following examples, formulation A is the commerical water reducing strength enhancing admixture, POZZOLITH POLYHEED- Master Builders Cleveland, Ohio, a low-retardation lignosulphonate-based water reducer, supplied as an aqueous solution containing 39% active material. 
     Formulation C is the commerical accelerating admixture, POZZOLITH 555A-Master Builders, a calcium nitrate-based chloride free accelerator supplied as an aqueous solution containing 48.7% active material. 
     The cement used was Kaiser Cement Type I/II with a 15% substitution of Jim Bridger fly ash (CF517 @70° F.)*. *CF=cement factor (Total cementive content) in pounds per cubic yard at 70° F. 
     The amounts of concrete used in the experiments was based upon the following cubic yard formulation: 
     438.7 lbs cement 
     78.7 lbs fly ash 
     1455.7 lbs sand 
     1698.7 lbs stone 
     295 lbs water 
     The tests were carried out in 5 gallon containers (approximately 2 cu. ft.). The amount of materials added to the concrete is based upon 100 lbs of cement, e.g., 80 oz=80 oz/100 lbs of cement. 
     The procedure for the experiments was as follows: 
     On the first day, the concrete mixtures were prepared with or without an admixture. Each concrete mixture was then put into the 5 gallon container for approximately 2 hours. After 2 hours, the retarder formulation was added to each container, and the contents mixed. 
     On the second day, the contents of the container were mixed with fresh concrete at a ratio of one part of the retarded concrete to five parts of fresh concrete (1:5) . The accelerator formulation was then added and the concrete mixture was tested for % air, ROH and compressive strengths. All experiments were compared with a plain concrete reference. 
     Example I 
     A number of concentrations of, DEQUEST 2000 were evaluated either alone or with citric acid. The concrete mix was reactivated with 5 oz/100 lbs of cement of composition A and 50 oz/100 lbs of cement of composition C. The results are shown in Table I. 
     
                       TABLE I                                                     
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                         Compressive                                      
Retarder                 Strength lbs/in.sup.2                            
Formula          Dose    ROH*    14 D**                                   
                                       28 D                               
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#1)  DEQUEST 2000    80 oz.  --    4124  5532                             
     .3182 #/100# cement                                                  
#2)  DEQUEST 2000    80 oz.  --    3935  5256                             
     .2273 #/100# cement                                                  
#3)  DEQUEST 2000    80 oz.  --    4560  6132                             
     .3182 #/100# cement                                                  
     citric acid                                                          
     .2000 #/100# cement                                                  
#4)  Plain cement    --      5.5 hrs.                                     
                                   3769  4619                             
     reference                                                            
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 *ROH = Rate of Hardening (initial set)                                   
 **D = Day, e.g., 14 D = 14 Days                                          
 
    
     Example II 
     Various DEQUEST retarder materials were evaluated with citric acid, Each DEQUEST material was tested at 0.3182 lbs/100 lbs of cement. The amount of citric acid (100% active material ) remained constant at 0.2000 lbs/100 lbs of cement. The DEQUEST material and citric acid were added to the concrete as a 40 oz/100 lbs of cement aqueous solution. 
     The cement mix was reactivated with 5 oz./100 lbs. of cement of composition A and 50 oz./100 lbs. of cement of composition C. The results are shown in Table II. 
     
                       TABLE II                                                    
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                         Compressive                                      
Retarder                 Strength lb/in.sup.2                             
Formula         % Air   ROH      1 D   7 D                                
______________________________________                                    
Plain Cement     .7     5.500 hrs                                         
                                 1229  3638                               
Reference                                                                 
1)  DEQUEST 2000 .3182  2.0   4.000 hrs                                   
                                     2181  6300                           
    Citric acid  .2000                                                    
2)  DEQUEST 2006 .3182  1.8   4.250 hrs                                   
                                     2097  5938                           
    Citric acid  .2000                                                    
3)  DEQUEST 2010 .3182  1.9   3.875 hrs                                   
                                     1992  5716                           
    Citric acid  .2000                                                    
4)  DEQUEST 2016 .3182  1.8   4.000 hrs                                   
                                     2047  5953                           
    Citric acid  .2000                                                    
5)  DEQUEST 2041 .3182  1.8   5.000 hrs                                   
                                     1725  6016                           
    Citric acid  .2000                                                    
6)  DEQUEST 2051 .3182  2.0   3.500 hrs                                   
                                     1960  5904                           
    Citric acid  .2000                                                    
7)  DEQUEST 2054 .3182  1.9   3.250 hrs                                   
                                     2047  5910                           
    Citric acid  .2000                                                    
8)  DEQUEST 2060 .3182  1.8   3.875 hrs                                   
                                     1912  5878                           
    Citric acid  .2000                                                    
9)  DEQUEST 2066 .3182  2.2   3.750 hrs                                   
                                     2210  --                             
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     Example III 
     In a preferred method of operating the process of the invention, when a ready-mix truck returns to a mixing plant with an unused portion of concrete, the temperature of the load is measured with a probe, the volume, of the load is estimated, and on the basis of these data and of the known characteristics of the concrete batch, the quantity of retarder necessary to keep the load usable until the next working day is calculated. Advantageously, this may be done by a suitably programmed microcomputer, and the required amount of retarder (preferably as an aqueous solution) may be automatically metered into the load. 
     The load is mixed for a short time, then left to stand without further mixing until the next working day. The required amount of fresh concrete is then mixed into the reclaimed concrete, the temperature is again measured, and the required amount of accelerator (and, if required, of water reducing agent) is calculated. Again, addition may be carried out under automatic computer control. In the following Table III are various retarding compositions in fluid ounces (fl. oz.) of solution per 100 lbs of cementitious material, of formulation (R) of this invention. The compositions are based on; 
     (1) Time from the initial batching of the concrete, 
     (2) The temperature of the concrete at the time of addition, and 
     (3) The length of time of retardation of set of the concrete desired, e.g., overnight (about 18-24 hours), or over a weekend (about 48-72 hours). 
     
                       TABLE III                                                   
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Overnight dosage                                                          
Concrete                                                                  
        for up to  for more than                                          
°F.                                                                
        1.5 cu. yd.                                                       
                   1.5 cu. yd.                                            
                              Weekend dosage                              
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90-99   55 fl. oz. 70 fl. oz. 145 fl. oz.                                 
80-89   50 fl. oz. 65 fl. oz. 135 fl. oz.                                 
70-79   40 fl. oz. 55 fl. oz. 125 fl. oz.                                 
60-69   35 fl. oz. 45 fl. oz. 115 fl. oz.                                 
50-59   25 fl. oz. 25 fl. oz. 105 fl. oz.                                 
40-49   20 fl. oz. 20 fl. oz.  95 fl. oz.                                 
32-39   15 fl. oz. 10 fl. oz.  85 fl. oz.                                 
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     The retarded concrete, after mixing with 5 parts of fresh concrete to 1 part of old retarded concrete, can be reactivated with the amount of accelerator formulation C (in fluid ounces of solution per 100 lbs. cementitious material) as shown in Table IV 
     
                       TABLE IV                                                    
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Concrete                                                                  
        Overnight retardation                                             
                        Weekend retardation                               
°F.                                                                
        accelerator dosage                                                
                        accelerator dosage                                
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80-89   30 fl. oz.       85 fl. oz.                                       
70-79   40 fl. oz.      105 fl. oz.                                       
60-69   50 fl. oz.      115 fl. oz.                                       
50-59   60 fl. oz.      120 fl. oz.                                       
40-49   70 fl. oz.      125 fl. oz.                                       
32-39   80 fl. oz.      130 fl. oz.                                       
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