Oil well cementing composition
This is a division of application Ser. No. 772,715, filed Feb. 28, 1977, which is a division of Ser. No. 654,497, Feb 2, 1976, now U.S. Pat. No. 4,047,567 which issued Sept. 13, 1977. 
     This invention relates to cement compositions and more particularly to the use of hydraulic cement compositions for sealing or cementing subterranean zones or subterranean zones penetrated by a well such as cementing the annular space in an oil well between the surrounding formation and casing. In particular the invention relates to an improved hydraulic cement composition for cementing zones at elevated temperatures in which the setting time of the cement composition is controlled or extended by the addition of a highly efficient non-gelling retarding agent which produces a hydraulic cement composition having a degree of predictability for the setting time. 
     Typically, the subterranean zones are cemented or sealed by pumping an aqueous hydraulic cement slurry into the zone. In cementing the annular space of an oil well, the cement slurry is pumped down the inside of the casing back up the outside of the casing through the annular space. Any cement slurry remaining in the casing is displaced and segregated using plugs and an aqueous displacement fluid. Frequently the high temperatures encountered is subterranean zones will cause premature setting of the hydraulic cement. This requires additives which extend or retard the setting time of the cement slurry so that there is adequate pumping time to which to place and displace the aqueous cement slurry in the desired zones. Previously known retarding agents are frequently unpredictable, typically produce erratic results with different brands of cement and frequently cause premature gelation of the cement slurry. Gelation refers to an abnormal increase of viscosity of the aqueous cement slurry to a value without a significant increase in the compressive strength of the cement composition. This increase in aqueous cement slurry viscosity makes the slurry difficult or impossible to pump at a viscosity of 70 poise or above which is defined as the set point herein. The cement composition has not attained an adequate compressive strength. 
     Prior art cement compositions and additives are described in the following list of 14 patents: 
     U.s. pat. No. 2,549,507 to Morgan et al 
     U.s. pat. No. 2,579,453 to Post et al 
     U.s. pat. No. 2,674,321 to Cutforth 
     U.s. pat. No. 2,676,170 to Patterson et al 
     U.s. pat. No. 2,680,113 to Adler et al 
     U.s. pat. No. 2,775,580 to Scarth 
     U.s. pat. No. 2,872,278 to Putnam et al 
     U.s. pat. No. 3,034,982 to Monroe 
     U.s. pat. No. 3,053,673 to Walker 
     U.s. pat. No. 3,135,727 to Monroe 
     U.s. pat. No. 3,344,063 to Stratton 
     U.s. pat. No. 3,748,159 to George 
     U.s. pat. No. 3,766,229 to Turner 
     U.s. pat. No. 3,821,985 to George. 
     Fundmentals of oil well cementing are described in the book PETROLEUM ENGINEERING DRILLING AND WELL COMPLETIONS, by Carl Gatlin, Prentice Hall, 1960. Background of and information on hydraulic cement compositions and additives can be found in the following books: 
     Lignin structure and reactions, advances in chemistry series, 1959, american Chemical Society, 1966; 
     Mechanical behavior of high polymers, by Turner Alfrey, Interscience Publishers, 1948; and 
     Hackh&#39;s chemical dictionary, 4th Ed., McGraw-Hill, 1969. 
     The above references and information cited therein are incorporated herein by reference to the extent necessary. 
     The hydraulic cement composition of this invention solve or eliminate many of the problems pointed out above. The hydraulic cement compositions of this invention do not have the gelation problem; the retarder composition is more efficient than prior art retarder compositions, the retarder has less variation with different brands of cement; cement compositions have much better predictability or reproducibiity of setting times with a given brand of cement; and hydraulic cement compositions have better rheology characteristics. Thus the improved cement compositions of this invention have practically eliminated the problems of unpredictability and irreproducibility of results which are particularly severe in high pressure deep wells where the temperatures may exceed 300° F. and 15,000 PSI. 
     The concentration of retarder composition of this invention required to produce the desired pumping time for or delay in setting of a cement slurry at a given circulating temperature is not as critical as with conventional lignosulfonate retarders. The thickening time at a given retarder concentration is less temperature dependent than with conventional retarders. This reduces the possibility of over retarded slurries at cooler temperatures encountered at the top of long liners or tie back strings. The retarder compositions of this invention provide the desired pumping times and allow earlier strength development. When cementing long strings this can reduce the WOC (waiting on cement to set) time by 8-12 hours. Thus, the retarder compositions of this invention are more predictable in performance than conventional lignosulfonate retarders especially with various brands of cement. The compositions of this invention act not only as retarders but also as a dispersing agent which can reduce fluid loss from gel type or high clay cement slurries. When the retarder composition of this invention is blended in a cement slurry, viscosity of the slurry decreases slightly and remains constant or does not increase significantly until the cement begins to set. This improvement in rheology or viscosity characteristics with improved predictability makes use of the compositions much easier than with conventional retarders. In addition, the retarder compositions of this invention are generally non-toxic, non-flammable, non-hazardous; compatible with cements, other additives and with most other well fluids and mix readily in aqueous systems with minimum agitation. 
     The high efficiency, non-gelling cement retarder composition of this invention has a high degree of predictability for controlling rheology and setting time of hydraulic cement comprising a low molecular weight sulfoalkylated lignin which is substantially sulfoalkylated in the lignin molecule at positions on the benzene ring which are ortho to the phenolic hydroxyl group. In the sulfoalkyl group the sulfonic acid group (--SO 3  H) is connected to the ortho position on the benzene ring by a methylene or substituted methylene group. This methylene or substituted methylene group is referred to herein as an alkylidene radical having one to five carbon atoms. This alkylidene radical with sulfonic acid radical can be represented by the formula (--R--SO 3  H) wheren R is the methylene group or alkyl portion having one to five carbon atoms and preferably one to three carbon atoms. 
     The unexpected properties of this retarder are thought to be due to the differences in average molecular weight or average molecular size and molecular structure. The evidence showing these differences is illustrated in the examples which show the unexpected properties. The sulfoalkylated lignin of this invention is a low molecular weight material having an average molecular weight or molecular size in the range of about 2,000-10,000 and preferably about 3,000-5,000. It is also thought to have a narrow molecular weight distribution. Prior art ligonsulfonate compounds have a molecular weight or molecular size of about 10,000 and higher and the sulfonate substituent or radical attached directly on the carbon atom of the lignin molecule which is in the alpha position of the phenyl propyl side chain. This phenyl propyl or aliphatic chain is attached at a position on the benzene ring which is para to the phenolic hydroxyl group discussed herein. For lignosulfonate the phenolic hydroxyl group can be replaced by an alkoxy group as indicated by R 1  --Ph--OR 2  wherein R 1  is the phenyl propyl side chain, Ph is phenyl or the benzene ring and R 2  is hydrogen or alkyl. The sulfoalkylated retarder composition of this invention has substantially all of the sulfoalkyl group (i.e., --R&#39;SO 3  H) in the position ortho to the phenolic hydroxyl group of the benzene ring of the lignin molecule. 
     The sulfoalkylated lignin retarder of this invention does not have a significant degree of sulfonation at the alpha carbon atom as do the prior art lignosulfonates. Thus, the sulfoalkylated lignin retarder of this invention is an entirely different chemical composition as shown by the unexpected and significantly different properties shown herein. The sulfoalkylated lignin retarder of this invention can be considered to be a sulfoalkylated lignin of high purity, low molecular weight with a narrow molecular weight distribution. This is thought to be due to the significantly different procedure used for its preparation. The sulfoalkylated lignin retarder for compositions of this invention can be prepared by catalytic oxidation of the sulfite liquor from a wood pulping process. This oxidation removes polysaccharides and wood sugars and substantially desulfonates the lignin molecule which is recovered as a residue. This purified lignin is separated from the liquor. The high purity, low molecular weight lignin molecule is then substantially sulfoalkylated by the addition of sulfonating agent such as sodium sulfite in the presence of an aldehyde or ketone having one to five carbon atoms at about 150-190° C. and 180-220 atmospheres. In this process, the aldehyde or ketone furnishes the alkylidene group which attaches at a vacant ortho position on the benzene ring in the lignin molecule and connects the sulfonate group through a methylene radical to the benzene ring at a position ortho to the free phenolic hydroxyl group. Some benzene rings may have more than one sulfoalkyl group attached and some benzene rings may have no sulfoalkyl substituents. The sulfur content of the sufoalkylated lignin is between about 3-10% and preferably 3-8%. 
     This sulfonate group can be in the form of the acid, a salt or combinations thereof. The salt can be in the form of ammonium or metal salt involving an alkali metal; an alkaline earth metal; or metals such as iron, copper, zinc, vanadium, titanium, aluminum, manganese, chromium, cobalt or nickel; or combinations thereof. The salts which are readily soluble in aqueous systems, such as those of the alkali metals, sodium and potassium, are preferred although the salts of alkaline earth metals and other metals can be used under certain circumstances. 
     The alkyl portion of the sulfonate substituent is derived from the aldehyde or ketone used in the sulfoalkylation step. Formaldehyde is a preferred alkyl source because it simply connects the sulfonate group to the ortho position by a one-carbon atom methylene group. Acetone would produce an alkylidene group having a methyl group on each side of the methylene group; methyl ethyl ketone would result in a methyl and an ethyl alkyl group attached to the methylene group; and propionaldehyde would result in an ethyl group attached to the methylene bridge. Theoretically, any aldehyde or ketone could be used for forming the alkylidene radical but the stereo chemistry and solubility must be considered in selecting the size and configuration of the aldehyde or ketone use for this component. A preferred sulfoalkylated lignin of this invention has a molecular weight in the range of about 3,000-4,000, a one carbon atom alkylidene radical and a sulfur content of about 3-8% by weight. 
     Another preferred hydraulic cement composition of this invention can be considered to be a modified low molecular weight sulfoalkylated lignin. This modified retarder composition is a combination of the high purity substantially sulfoalkylated lignin described above and at least one water soluble hydroxy carboxylic acid. These hydroxy carboxylic acids have a synergistic effect of increasing the effectiveness and operable temperature range of the basic retarder composition. The preferred carboxylic acids are substantially alphatic carboxylic acids and preferably polyhydroxy carboxylic acids having at least one terminal carboxy group which can be in the form of the acid, a salt or mixtures thereof as described above for the sulfonate groups. 
     Particularly preferred polyhydroxy carboxylic acids have a molecular weight in the range of about 125-250 and have a hydroxyl group attached to the carbon atom adjacent to the carboxy group as shown by the formula ##STR1## These carboxylic acids include gluconic acid, tartaric acid and equivalents thereof. These equivalents include the various stereoisomers of the above acids particularly the asymmetric or optically active isomers. Thus, the preferred group of hydroxy carboxylic acids are substantially linear aliphatic acids have about 4-10 carbon atoms, and preferably 4-8 carbon atoms. The molecular size and number of hydroxy and carboxylic groups will affect the water solubility. The hydroxy carboxylic acid is preferably present with the sulfoalkylated lignin in a weight ratio of acid to lignin preferably in the range of about 1:0.-5.0 and preferably in the range of about 1:0-3.0. 
     The hydraulic cement compositions of this invention are typically used in the form of an aqueous slurry of hydraulic cement with a concentration of retarder mixed in the aqueous slurry to control or delay the cement setting time so that it exceeds the pumping time with an adequate safety margin. Sufficient water is added to the slurry to make the composition pumpable. As used herein the hydraulic cement is typically a Portland cement which is set by the water of the slurry in the absence of air which is excluded by placement of the cement in the zone to be sealed. The low molecular weight sulfoalkylated lignin retarder of this invention is preferably present in the aqueous hydraulic cement slurry in a concentration up to about 2%, and preferably up to 1%, by weight based on the dry cement. Higher retarder concentrations and other cement can be used when necessary in unusual circumstances. A defoaming agent is typically added as are fluid loss additives, friction reducing additives, salts such as sodium chloride and potassium chloride, weighting additives and other conventional additives as described in the references cited above. Pozzolana cement, high alumina cement or high gel (high clay content) cement can be used for special applications. The low molecular weight sulfoalkylated retarder composition of this invention has high reproducibility and predictability when used with most high quality cements which are typically used in the petroleum industry. However, certain brands which are not manufactured to standard specifications, such as those which are not sufficiently calcined or having varying degrees of free lime remaining in the cement, will produce substantial variations from the standard high quality brands. It is not clear whether the free lime causes the problems or is merely an indication when the problems exist. These variations can be readily determined by preliminary tests which make even these substandard cements readily predictable and may merely require slightly higher retarder concentrations to offset the chemical composition variations of the cement or excess lime content. 
     In a preferred process for using the non-gelling hydraulic cement composition of this invention having a degree of predictability of setting time and containing the high efficiency retarder, the retarder composition is mixed with the hydraulic cement as an aqueous slurry with the retarder concentration up to about 2% on a dry cement weight basis. The hydraulic cement mixture is pumped without gelation into the zone to be sealed or cemented and the hydraulic cement mixture is maintained in the zone until an adequate compressive strength is attained. In this process the retarder concentration preferably up to about 2% on a dry cement weight basis is calculated to control the setting time of the hydraulic cement slurry to exceed the pumping time within an adequate safety margin. Due to the higher efficiency of the retarder and greater predictability of the hydraulic cementing compositions of this invention, the portion of the safety margin previously required for these variations can be substantially reduced. The safety margin now need primarily allow time only for unexpected equipment difficulties. This reduction in the safety margin time or time which the typical oil drilling rig is waiting for the cement to set can result in a substantial economic advantage due to the higher efficiency and predictability of the hydraulic cement compositions of this invention. The modified low molecular weight sulfoalkylated lignin of this invention or the combination of the sulfoalkylated lignin with the hydroxy carboxylic acids improve the efficiency and predictability of the compositions of this invention even more and therefore are preferably used. The basic sulfoalkylated lignin retarder composition of this invention can be used up to a temperature (i.e., BHCT) slightly in excess of about 210° F. and the modified retarder composition containing the hydroxy carboxylic acids can be used up to a temperature of about 400° F. 
     The molecular weight of the sulfoalkylated portion of the composition of this invention is determined by diffusion techniques. These differences between the sulfoalkylated lignin compositions of this invention and the prior art lignosulfonates are shown by the examples. 
     The following examples serve to illustrate various embodiments of the invention and enable one skilled in the art to practice the invention. Parts, percentages, proportions and concentrations are by weight unless indicated otherwise. 
     Samples of calcium (CaLS) and sodium lignosulfonates (NaLS) and a preferred sulfomethylated lignin (SML) composition of this invention were analyzed chemically by spectroscopy using X-ray, infrared, and ultraviolet radiation techniques. The samples were prepared and analyzed by standard procedures such as those described in ABSORPTION SPECTROSCOPY, by Robert P. Bauman, John Wiley &amp; Sons, Inc., 1962, which is incorporated herein by reference to the extent necessary. X-ray diffraction merely showed that both the lignosulfonate and sulfoalkylated lignin were noncrystalline. 
     Chemical analysis indicated the following constituents by weight: 
     
         ______________________________________                                    
% C          % H.sub.2  % Ca       % S                                    
______________________________________                                    
CaLS    39.1     4.3        7.6      3.9                                  
NaLS    42.2     4.6        0.3      7.4                                  
SML     45.0     3.8        0.2      6.2                                  
______________________________________                                    
 
    
     The sulfur content of NaLS and SML was thought to include some inorganic sulfur (e.g. CaSO 4 ) entrained from cation exchange or sulfonation liquor. 
     For ultraviolet (UV) technique which scanned 190-360 millimicrons (mμ) for both NaLS and SML showed a major peak at about 202≧205 millimicrons with shoulder or decreasing peaks at about 230 and 310-320 millimicrons. The samples were in water at a 0.02 gram per liter concentration and were run in a one cm path length cell. 
     The infrared (IR) transmittance scan from 2.5-30 microns or 300-400 cm -1  showed peaks at the following wave lengths (λ) in cm -1  : 
     NaLS:3440; 2940; 2840*; 1590; 1495; 1450; 1415; 1250*; 1200; 1140*; 1035; 930*; 640 and 590. 
     SML: 3440; 2940; 2840; 1675; 1590; 1495; 1450; 1415; 1355; 1250*; 1200; 1140*; 1070; 1035; 930*; 850; 775; 735; 590 and 525. 
     The starred values (*) are shoulder peaks or peaks which are not very distinct. Samples for the IR scan were mulled in NUJOL mineral oil and run between salt plates. 
    
    
     EXAMPLES 
     For the following examples each sample was prepared by measuring an 800-gram portion of the designated dry cement into a cylindrical container of approximately 800 milliliters volume. Dry or powdered additive are designated as a percentage of the weight of the dry powdered cement unless indicated otherwise. Dry powdered additives are measured and blended with cement. A portion of tap water equal to the weight percentage of the dry cement is slurried with the dry cement and additives with vigorous mixing. The slurry is stirred for an additional 30 seconds at a high rate. Liquid additives are blended into the water. Samples were tested according to standard procedures set forth in API Method RP-10B which is incorporated herein by reference. 
     For thickening time tests a sample portion is stirred in a container of about 500 milliliters at a temperature and pressure schedule determined by API method RP 10B. The container is heated from ambient temperature under pressure. It contains a direct reading consistometer which is calibrated with a potentiometer calibrating device to read directly in units of consistency (API-RP-10B). The set time or setting point is the time or point at 70 units of consistency or viscosity. 
     API Method RP-10B provides the following casing schedule for bottom hole circulating temperature (BHCT) and bottom hole static temperature (BHST) at the indicated depths: 
     
         ______________________________________                                    
Depth (ft.)  BHCT (° F.)                                           
                           BHST (° F.)                             
______________________________________                                    
 8,000 (2440 m)*                                                          
             125 (51.67° C.)*                                      
                           200 (93.33° C.)*                        
10,000 (3050 m)                                                           
             144 (62.22° C.)                                       
                           230 (110.00° C.)                        
12,000 (3660 m)                                                           
             172 (77.78° C.)                                       
                           260 (126.67° C.)                        
14,000 (4270 m)                                                           
             206 (96.67° C.)                                       
                           290 (143.33° C.                         
15,000 (4575 m)                                                           
             226 (107.78° C.)                                      
                           305 (151.66° C.)                        
16,000 (4880 m)                                                           
             248 (120.00° C.)                                      
                           320 (160.00° C.)                        
18,000 (5490 m)                                                           
             300 (148.89° C.)                                      
                           350 (176.67° C.)                        
20,000 (6100 m)                                                           
             340 (171.11° C.)                                      
                           380 (193.33° C.)                        
22,000 (6710 m)                                                           
             380 (193.33° C.)                                      
                           410 (210.00° C.)                        
______________________________________                                    
 Metric Equivalents                                                       
 
    
     Fluid loss is the number of milliliters or cubic centimeters of liquid forced through No. 50 Whatman filter paper or through 325 mesh screen according to API publication RP-10B (Section 8). 
     
                       TABLE I                                                     
______________________________________                                    
Predictable Behavior                                                      
______________________________________                                    
Lone Star Class H Cement                                                  
38% H.sub.2 O                                                             
         Thickening Times                                                 
         Hours:Minutes                                                    
SML*     API Casing Simulation Tests                                      
% Retarder                                                                
         8,000&#39;    10,000&#39;   12,000&#39; 14,000&#39;                              
______________________________________                                    
0.20     2:35      2:04      1:33    --                                   
0.25     4:20      2:37      --      --                                   
0.30     5:50      3:11      2:31    1:58                                 
0.35     --        5:20      --      --                                   
0.40     --        --        4:12    3:01                                 
0.50     --        --        7:18    3:47                                 
0.60     --        --        --      4:09                                 
0.70     --        --        --      5:12                                 
Lone Star Class H Cement                                                  
46% H.sub.2 O                                                             
0.16     2:43      --        --      --                                   
0.20     --        2:25      2:15    1:55                                 
0.24     3:51      --        --      --                                   
0.30     6:40      3:28      3:01    2:32                                 
0.34     --        --        3:58    --                                   
0.35     --        6:13      --      --                                   
0.38     --        --        4:17    --                                   
0.40     --        11:22     --      3:32                                 
0.44     --        --        5:37    --                                   
0.60     --        --        --      6:10                                 
______________________________________                                    
 *Sulfomethylated lignin retarder.                                        
 
    
     Increasing the retarder concentration results in corresponding increase in thickening time until a saturation point is reached. Beyond this point, slight increases in the retarder concentration result in greatly increased thickening times. 
     
                       TABLE II                                                    
______________________________________                                    
Set Times Obtained with Commercially Available                            
Calcium Lignosulfonate and the Sodium Salt of                             
Sulfomethylated Lignin.sup.a                                              
                       Percent  Set Times -                               
              Percent  Sodium   Hours:Minutes                             
              Retarder Chloride API Casing                                
              (by wt.  (by wt.  Simulation Tests                          
206° F.Cement)  water)   14,000&#39;                                   
______________________________________                                    
Sulfomethylated Lignin                                                    
              0.3      0        1:58                                      
              0.4      0        3:01                                      
              0.5      0        3:47                                      
              0.6      0        4:09                                      
              0.7      0        5:12                                      
Calcium Lignosulfonate                                                    
              0.3      0        3:25                                      
              0.4      0        4:05                                      
              0.5      0          1:34.sup.b                              
              0.6      0          1:35.sup.b                              
Sulfomethylated Lignin                                                    
              0.3      18.0     1:44                                      
              0.4      18.0     2:27                                      
              0.5      18.0     2:45                                      
              0.6      18.0     3:42                                      
              0.7      18.0     4:33                                      
              0.8      18.0     5:12                                      
Calcium Lignosulfonate                                                    
              0.2      18.0       1:32.sup.b                              
              0.3      18.0       1:40.sup.b                              
              0.4      18.0       1:48.sup.b                              
              0.5      18.0       2:05.sup.b                              
              0.6      18.0       2:40.sup.b                              
______________________________________                                    
 .sup.a All slurries consisted of 800 grams Lone Star Class H Cement with 
 304 grams (38%) water, and indicated amounts of additive and sodium      
 chloride.                                                                
 .sup.b Slurry gelation was observed, i.e., viscosity reached 70 units of 
 consistency but slurry had not developed significant compressive strength
 at that time. Others reached a viscosity of 70 units and set with        
 compressive strength at approximately the same time.                     
 
    
     At higher tempertures slurries containing the conventional retarder tend to form unpumpable heavy gels prior to development of significant compressive strength, however, use of the sulfomethylated compound yielded slurries which were well dispersed until final hard set of the cement was obtained. This is illustrated in Table II which lists the set time and percent added retarder for both fresh and salt water slurries containing either the commercially available calcium salt of lignosulfonate or the sodium salt of the new sulfomethylated compound. As noted in the table, many of the slurries containing the calcium salt tended to form heavy gels (i.e., slurry is unpumpable and thus, considered set when the viscosity reaches 70 units of consistency even though it may have gelled with no compressive strength at that time); this results in an erratic dependence of set time on retarder concentration. For example, in the fresh water slurries, increases in retarder concentration in excess of approximately 0.4% (Table II) result in decreased rather than the expected increased set times; this effect is not found for the new compound which shows a reasonable set time increase as the retarder concentration is increased in both fresh and salt water slurries. 
     
                       TABLE III                                                   
______________________________________                                    
Predictable Behavior One Cement to Another                                
Effect of Cement Brand on Set Time.sup.a                                  
                        Percent                                           
                        Additive Set Time -                               
                        (by wt.  Hours:Minutes                            
                        of       API Casing                               
Type of Cement                                                            
206° F.ditive    cement)  14,000&#39;                                  
______________________________________                                    
Lone Star Class H                                                         
            Sulfomethylated                                               
(Maryneal).sup.b                                                          
            Lignin      0.5      3:37                                     
Lone Star Class H                                                         
            Calcium                                                       
(Maryneal).sup.b                                                          
            Lignosulfate                                                  
                        0.5       1:34.sup.h                              
Lone Star Class H                                                         
            Sulfomethylated                                               
(New Orleans).sup.c                                                       
            Lignin      0.5      2:45                                     
Lone Star Class H                                                         
            Calcium                                                       
(New Orleans).sup.c                                                       
            Lignosulfate                                                  
                        0.5       0.40.sup.h                              
Trinity Class H.sup.d                                                     
            Sulfomethylated                                               
            Lignin      0.5      2:46                                     
Trinity Class H.sup.d                                                     
            Calcium                                                       
            Lignosulfate                                                  
                        0.5       3:02.sup.h                              
Southwestern                                                              
            Sulfomethylated                                               
Class H.sup.e                                                             
            Lignin      0.5      3:19                                     
Southwestern                                                              
            Calcium                                                       
Class H.sup.e                                                             
            Lignosulfate                                                  
                        0.5      4:05                                     
Oklahoma Class H.sup.f                                                    
            Sulfomethylated                                               
            Lignin      0.5      3:00                                     
Oklahoma Class H.sup.f                                                    
            Calcium                                                       
            Lignosulfate                                                  
                        0.5       3:45.sup.h                              
Dyckerhoff Class B.sup.g                                                  
            Sulfomethylated                                               
            Lignin      0.5      2:44                                     
Dyckerhoff Class B.sup.g                                                  
            Calcium                                                       
            Lignosulfate                                                  
                        0.5      2:45                                     
______________________________________                                    
 .sup.a Slurries consisted of 800 grams indicated cement, 304 grams (38%) 
 water (by wt. of cement), and additive with the exception of the slurries
 containing Dyckerhoff Class B which contained 368 grams (46%) water.     
 .sup.b Cement manufactured by Lone Star Industries, Inc., Maryneal, Texas
 .sup.c Cement manufactured by Lone Star Industries, Inc., New Orleans,   
 Louisiana.                                                               
 .sup.d Cement manufactured by Trinity, Portland Cement Division, Dallas, 
 Ft. Worth, Houston, Texas.                                               
 .sup.e Cement manufactured by Southwestern Portland Cement Company, El   
 Paso, Texas.                                                             
 .sup.f Cement manufactured by OKC Corporation, Pryor, Oklahoma.          
 .sup.g Cement manufactured by Dyckerhoff Zementwerke AG,                 
 Wiesbaden-Biebrich, Germany.                                             
 .sup.h These slurries gelled prior to hard set.                          
 
    
     At constant concentration of the new retarder, reasonably consistent set times are obtained for slurries containing cements produced by different manufacturers (Table III). This contrasts with the similar results for calcium lignosulfonate which vary drastically from one cement to another. 
     
                                           TABLE IV                                
__________________________________________________________________________
Slurry Gelation Effect                                                    
Viscosity versus Pumping Time for the Slurries                            
Containing Calcium Lignosulfonate or the Sodium                           
Salt of Sulfomethylated Lignin                                            
                         Pumping Times                                    
                         Hours:Minutes                                    
                                 Viscosity                                
                    Percent                                               
                         14,000&#39; API                                      
                                 In Units of                              
Type of Cement Additive.sup.d                                             
                    Additive                                              
                         Casing - 206° F.                          
                                 Consistency.sup.e                        
__________________________________________________________________________
Lone Star Class H (Maryneal)                                              
               SML  0.5  0:00    9                                        
                         0:30    6                                        
                         0:45    6                                        
                         1:00    6                                        
                         1:15    6                                        
                         1:30    6                                        
                         2:00    12                                       
                         2:15    21                                       
                         3:00    26                                       
                         3:15    29                                       
                         3:30    31                                       
                          3:47.sup.b                                      
                                 70                                       
               NaLS 0.5  0:00    1                                        
                         0:30    4                                        
                         0:45    13                                       
                         1:00    37                                       
                         1:15    41                                       
                         1:30    45                                       
                          1:34.sup.c                                      
                                 70                                       
__________________________________________________________________________
 .sup.a Slurries consisted of cement, 38% water and additive.             
 .sup.b Slurry reached a viscosity of 70 units and set with compressive   
 strength at approximately the same time.                                 
 .sup.c Slurry reached a viscosity of 70 units but had no compressive     
 strength until approximately two hours later.                            
 .sup.d SML is sulfomethylated lignin and NaLS is sodium lignosulfonate.  
 .sup.e Consistency measured directly in units of consistency according to
 API publicaton RP-10B.                                                   
 
    
     
                       TABLE V                                                     
______________________________________                                    
Lower Temperatures                                                        
Set Times Obtained with Calcium Lignosulfonate                            
and the Sodium Salt of Sulfomethylated Lignin                             
          Percent                                                         
          Retarder                                                        
                 Set Times - Hours:Minutes                                
          (by wt.                                                         
                 API Casing Simulation Tests                              
Retarder    Cement)  10,000&#39;     12,000&#39;                                  
______________________________________                                    
Sulfomethylated                                                           
Lignin.sup.a                                                              
            0.3      --          2:30                                     
            0.4      --          3:57                                     
            0.5      --          8:00                                     
Calcium                                                                   
Lignosulfonate.sup.a                                                      
            0.3      --          3:10                                     
            0.4      --          2:21                                     
            0.6      --          1:40                                     
Sulfomethylated                                                           
Lignin.sup.b                                                              
            0.08     2:58        --                                       
            0.12     3:29        --                                       
            0.16     4:00        --                                       
            0.20     4:50        --                                       
            0.24     6:33        --                                       
Calcium                                                                   
Lignosulfonate.sup.b                                                      
            0.40      1:44.sup.c --                                       
            0.80      3:20.sup.c --                                       
______________________________________                                    
 .sup.a Slurries consisted of Dyckerhoff Class G, 44% water and indicated 
 additive.                                                                
 .sup.b Slurry consisted of Longhorn Class H Cement with 44% water, 35%   
 coarse silica flour (60-140 mesh), 0.75% CFR-2 friction reducer and 18%  
 sodium chloride salt. CFR-2 is beta-naphthalene sulfonic acid condensed  
 with formaldehyde and mixed with 10% polyvinyl pyrrolidone. CFR-2 is     
 described in U.S. Pat. No. 3,359,225 which is incorporated herein by     
 reference.                                                               
  .sup.c Slurries showed severe gelation effects.                         
 
    
     
                       TABLE VI                                                    
______________________________________                                    
Compressive Strength                                                      
Class H Cement with 38% Water                                             
Retarder Concentration Giving 4.0 Hr. Pumping                             
Time on 12,000 ft. Schedule                                               
Slurries Pumped 2 hrs. on 12,000 ft. Schedule                             
and placed in Autoclaves at Indicated                                     
Temperature                                                               
Compressive Strength     Compressive Strength                             
Using Conventional       Using SML                                        
Lignosulfonate Retarder  Cement Retarder                                  
(PSI)         Temperature                                                 
                         (PSI)                                            
8 hrs 12 hrs  24 hrs  ° F.                                         
                               8 hrs 12 hrs                               
                                           24 hrs                         
______________________________________                                    
 NS*  290     2260    170       650  1690  2790                           
NS    2080    2660    200      1010  2020  3980                           
NS    2270    2840    230      1670  2800  4260                           
1360  3480    3310    260      2040  3660  5420                           
______________________________________                                    
 *Not Set                                                                 
 
    
     Compressive strength tests were run on slurries containing calcium lignosulfonate or sulfomethylated lignin. The cement employed in these tests was Lone Star Class H. In these tests, slurries containing retarder to give four hour pumping times on a 12,000&#39; casing schedule were used. The slurries were pumped two hours at a 12,000&#39; casing schedule and placed in autoclaves at four different temperatures to simulate the actual conditions encountered from the top to the bottom of a cement column in a well. The compressive strengths were then determined after 8, 12 and 24 hours according to API publication RP-10B (Section 6). After 8 hours, the slurries containing lignosulfonate had not set at the lower temperatures. However, the slurries containing sulfomethylated lignin were all set with significant strengths. The sulfomethylated slurries consistently showed more rapid strength development throughout these tests. 
     
                                           TABLE VII                               
__________________________________________________________________________
Compatibility With Fluid Loss Additives                                   
Compatibility of New Sulfomethylated Lignin and Common Fluid Loss         
Additives.sup.a                                                           
                    Percent                                               
                         Fluid Loss Additive                              
                                     Sodium                               
Consistometer Readings                                                    
                    Retarder                                              
                         1.sup.b                                          
                               2.sup.c                                    
                                     Chloride                             
                                           Fluid                          
at 100° F. (Poise)                                                 
                    By Wt.                                                
                         % By Wt.                                         
                               % By Wt.                                   
                                     % By Wt.                             
                                           Loss                           
Initial                                                                   
      Final Retarder                                                      
                    Cement                                                
                         Cement                                           
                               Cement                                     
                                     Water (cc)                           
__________________________________________________________________________
            Sulfomethylated                                               
9     8     Lignin  0.5  0.6   0     0     44                             
            Calcium                                                       
9     10    Lignosulfonate                                                
                    0.5  0.6   0     0     141                            
            Sulfomethylated                                               
10    10    Lignin  0.5  0.6   0     18.0  98                             
            Calcium                                                       
10    10    Lignosulfonate                                                
                    0.5  0.6   0     18.0  188                            
            Sulfomethylated                                               
12    12    Lignin  0.5  0     0.6   0     38                             
            Calcium                                                       
10    10    Lignosulfonate                                                
                    0.5  0     0.6   0     137                            
            Sulfomethylated                                               
12    12    Lignin  0.5  0     0.6   18.0  82                             
11    11    Lignosulfonate                                                
                    0.5  0     0.6   18.0  154                            
__________________________________________________________________________
 .sup.a All slurries contained Lone Star Class H Cement, 28% water, and   
 indicated amounts of retarder, Halliburton fluid loss additive, and sodiu
 chloride. After mixing, the slurries were stirred on the Halliburton     
 Consistometer for 20 minutes at 100° F. and fluid loss deterinatio
 conducted at 100 PSI pressure on a 325 mesh screen at the same           
 temperature.                                                             
 .sup.b 56% HEC (hydroxyethyl cellulose) with 44% CFR-2.                  
 .sup.c 60% HEC, 20% defoamer with 20% CFR-2.                             
 
    
     
                                           TABLE VIII                              
__________________________________________________________________________
Dispersant and Fluid Loss Properties in Gel Cement Slurries               
Class H Cement                                                            
12% Gel                                                                   
11.46 gal. water/sack                                                     
                                  Fluid Loss                              
                                  cc/30 Min.                              
                                  100 PSI                                 
        % Addition                                                        
              Fann Data           No. 50                                  
                                       1000 PSI                           
        (By wt.                                                           
              Shear Stress lb/ft.sup.2  at 80° F.                  
                                  Whatman                                 
                                       325 Mesh                           
Retarder                                                                  
        Cement)                                                           
              600 RPM                                                     
                   300 RPM                                                
                        200 RPM                                           
                             100 RPM                                      
                                  Paper                                   
                                       Screen                             
__________________________________________________________________________
Sulfomethylated                                                           
Lignin  0     1.22 1.16 1.12 1.05 10   372                                
        0.34  0.47 0.34 0.31 0.26 132  265                                
        0.52  0.42 0.27 0.21 0.17 104  188                                
Calcium Sodium.sup.a                                                      
Lignosulfonate                                                            
        0.34  0.58 0.47 0.43 0.37 149  258                                
        0.52  0.69 0.56 0.51 0.46 113  217                                
__________________________________________________________________________
 .sup.a A mixed calcium-sodium lignosulfonate is used in gel cement       
 slurries instead of simple calcium lignosulfonate due to the tendency of 
 the latter to gel slurries of this type.                                 
 
    
     Sulfomethylated lignin functions in gel cement slurries as a dispersant and fluid loss additive. Previously, two separate retarders were required; one for non-gel slurries which was calcium lignosulfonate and another for gel slurries which was calcium sodium lignosulfonate. 
     
                       TABLE IX                                                    
______________________________________                                    
Extension with Tartaric Acid                                              
Set Times Obtained with a Mixture of the Sodium                           
Salt of Sulfomethylated Lignin and Tartaric Acid                          
in a 2:1 Weight Ratio*                                                    
         Set Times                                                        
% Retarder                                                                
         Hours:Minutes                                                    
(By Wt.  API Casing Simulation Tests                                      
Cement)  16,000&#39;   18,000&#39;   20,000&#39; 22,000&#39;                              
______________________________________                                    
0.4      1:55      --        --      --                                   
0.5      4:20      --        --      --                                   
0.6      5:57      1:40      --      --                                   
0.8      --        2:31      --      --                                   
0.9      --        3:43      --      --                                   
1.0      --        4:34      --      --                                   
1.1      --        5:13      --      2:00                                 
1.2      --        --        3:43    --                                   
1.3      --        --        --      2:28                                 
1.6      --        --        5:10    --                                   
1.8      --        --        6:32    3:12                                 
2.0      --        --        --      3:25                                 
2.6      --        --        --      4:10                                 
______________________________________                                    
 *All slurries consisted of Lone Star Class H Cement, 35% SSA-1, 54% water
 and indicated amounts of retarder. SSA-1 is fine silica flour which is   
 added to cement slurries at high temperature to prevent strength         
 retrogression. Over 97% of the silica particles pass through a 200-mesh  
 (U.S. Std. Sieve Series) screen.                                         
 
    
     
                       TABLE X                                                     
______________________________________                                    
Extension of Set Times of Slurries Containing                             
Sulformethylated Lignin by the Addition of Borax                          
Percent    Percent                                                        
Sulfomethylated                                                           
           Borax     Set Time - Hours:Minutes                             
Lignin (By Wt.                                                            
           (By Wt.   API Casing Schedule                                  
Cement     Cement)   15,000&#39;     16,000&#39;                                  
______________________________________                                    
0.7        0.6       3:00        --                                       
0.8        0.6       4:22        --                                       
0.9        0.6       5:12        --                                       
0.4        0.7       --          1:54                                     
0.6        0.7       --          3:54                                     
0.8        0.7       --          5:20                                     
0.95       0.7       --          7:10                                     
______________________________________                                    
 
    
     Set times obtained with sulfomethylated lignin can be extended by the addition of boric acid or water soluble salt of boric acid (e.g., salts of ammonia, alkali or alkaline earth metals). This extension makes possible the use of the sulfomethylate lignin retarder at higher temperatures. Examples of extenders of this type are: 
     (1) Boric acid, 
     (2) Na 2  B 4  O 7 .sup. . 10 H 2  O (Borax), 
     (3) Na 2  B 5  O 8  8.sup. . 5 H 2  O, 
     (4) kb 5  o 8 .sup. . 4 h 2  o, 
     (5) li 1  B 5  O 8 .sup. . 5H 2  O, 
     (6) naBO 2 .sup. . 4H 2  O, 
     similar compounds and mixtures thereof.