Abstract:
Bitumen content of tailings or sludge obtained from processing of tar sands is quickly determined by a two step process wherein (1) clay mineral content is determined by adsorption of methylene blue and this value correlated to adsorbed organic material, (2) the content of total organic material is determined by a chromic acid oxidation, and the difference in these values gives the bitumen content.

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to a method for the rapid determination of bitumen in the sludge generated by extraction of hydrocarbon oil from tar sands and similar materials. 
     Bitumen determinations are conventionally made only after lengthy laboratory procedures requiring at least 48 hours. These procedures include a technique of drying the sludge overnight, grinding, weighing, extracting with a mixture of carbon bisulfide, acetone, and methanol or other solvents in a soxhlet extractor, drying and a final weighing. While such a method gives good results it is a very long and tedious procedure. In tar processing plants it is important that bitumen analyses be made as quickly as possible in order that no holdup of sludge treatment occur. This invention provides such a rapid method. 
     SUMMARY OF THE INVENTION 
     In accord with the method of the invention, an analysis of the sludge to determine both clay mineral content and total organic content is made; the clay mineral content is used as a basis to determine organics adsorbed by clay minerals and this value is then subtracted from the total organics present as determined by a chromic acid oxidation. The analyses are easily made by titration techniques enabling the entire procedure to be completed in about one hour. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 shows a curve for the relationship of minerals content to de-aired density. 
     FIG. 2 is a curve used for determination of clay minerals by methylene blue titration. 
     FIG. 3 is a curve showing the correlation of adsorbed organic materials from clay minerals. 
    
    
     DETAILED DESCRIPTION 
     The first step of the two step method, as indicated, involves the determination of the clay minerals content of the tailings or sludge resulting from the extraction of bitumen from tar sands and similar materials and is disclosed in Canadian application Ser. No. 365,173 filed Nov. 21, 1980 and U.S. application Ser. No. 312,606 filed Oct. 19, 1981, which disclosure is hereby incorporated by reference. The value of clay mineral content obtained by this method is converted to adsorbed organics by multiplying the clay minerals content by 0.0234 as shown by FIG. 3. 
     The second step of the invention is an oxidation of the sludge with chromic acid to obtain the amount of total organics present and this is done by titration with an appropriate indicator such as Ferroin. Other indicators may be used, but tests with diphenylamine as indicator are much less accurate. 
     The test methods are as follows: 
     Step I 
     Determination of Organics Adsorbed by Clay Minerals in Sludge 
     A known weight of sludge or tailings (5±1 g) is taken, dispersed in about 50 ml water and acidified with 2 ml of 10% H 2  SO 4 . This solution is titrated in 1 ml increments to the end point with methylene blue dye (0.01 N). The end point is reached when the sample has adsorbed all the dye possible, and the excess passes into the water solution. This point is visualized by placing a drop of the sludge suspension on filter paper by means of the blunt end of a 1 ml pipette. Before the excess is reached, a blue dot is formed, surrounded by a wet, colorless, circular area. When an excess of dye is attained, the blue color begins to extend into the wet area. The excess must remain after two minutes of shaking the titrated sample to ensure complete adsorption. 
     In order to establish empirical curves with which to correlate the methylene blue titration with clay mineral content, a direct determination of percent clay mineral is made by X-ray diffraction techniques with the particular type of sludge to be analyzed. In order to estimate the clay minerals in the tailings or sludge it is necessary to first establish their minerals content and relate this to deaired density. FIG. 1 shows such a curve where actual mineral content was obtained by the oven drying technique. The procedure for obtaining de-aired solids and preparing the empirical curves for the methylene blue titration as adsorbed organics follows: 
     1. The exact volume of a 25-ml pycnometer is determined by weighing empty and filled with distilled water. 
     2. A sample sludge is deaired under vacuum (74 cm Hg) for one hour. 
     3. The deaired sludge is carefully poured into the pycnometer and weighted--thus the weight and volume of the sludge are known. 
     4. The density is calculated: 
     
         density=[weight (g)/volume (ml)] 
    
     5. From the relationship of deaired density to percent mineral solids (w/v) given in FIG. 1, the amount of mineral solids in the sludge sample is found. The slope of this linear relationship may be somewhat different than theoretically expected, because of the presence of small amounts of dissolved or free gases still retained in the samples, even after deairing. 
     6. Several samples of a known volume or weight of sludge are taken to contain approximately 1-2 g mineral solids (as determined in step 5), acidified and titrated with methylene blue as described above. 
     7. The amount of clay minerals as determined by the x-ray diffraction technique versus the amount of methylene blue used may be plotted to obtain FIG. 2. These correlation curves are plotted from the analysis of numerous tailings and sludge samples. About 200 samples were analyzed to obtain the data in FIG. 2. 
     8. Samples with unknown content of clay or clay minerals may then be titrated with methylene blue and the clay mineral content obtained from the curves. 
     9. A known weight of mineral solids obtained after soxhlet extraction of an oven dried sample of the sludge is treated with hydrogen peroxide and heated to oxidize the adsorbed organics. The percent adsorbed organics is obtained from the weight loss of the treated sample and the percent adsorbed organics is plotted against percent clay minerals to obtain an empirical correlation, as shown in FIG. 3. 
     Step II 
     Determination of Total Organics by Chromate Oxidation 
     This method is disclosed in the text &#34;Diagnosis And Improvement of Saline Alkaline Soils,&#34; U.S. Dept. of Agriculture Handbook N.Y. 60, February 1954, L. A. Richards, Editor, pages 105-106, which is hereby incorporated by reference. 
     Organic Determination with the Ferroin Indicator 
     A. Preparation of Solutions 
     1. Ferrous Sulfate 0.5 N: dissolve 140 g FeSO 4 .7H 2  O in 500 mls distilled water. Then add 15 mls concentrated sulfuric acid, and dilute to 1 liter. 
     2. Potassium Dichromate 1.0 N: dilute 49.04 g K 2  Cr 2  O 7  to 1 liter with distilled water. 
     3. Ferroin indicator: dissolve 0.495 g indicator in 100 mls distilled water. 
     B. Test Procedure 
     Weigh about 0.3 g sludge into a 500 ml Erlenmyer flask. Pipette 20 mls 1 N K 2  Cr 2  O 7  into flask, swirl, and then add 40 mls concentrated sulfuric acid. Swirl the flask, insert the thermometer, and heat gently so that a temperature of 150° C. is reached in about 1 minute. Swirl continuously during this heating time to prevent local overheating, then remove from heat, and allow to cool to room temperature. Add 200 mls distilled water to the cooled mixture and 5 drops of the ferroin indicator. Titrate with FeSO 4  solution in a 50 ml burette from an olive green colour through Kelly green and blue-green to the first muddy brown colour. Note that the addition of the indicator itself does not change the colour of the solution. Note the volume of FeSO 4  delivered. 
     Calculations ##EQU1## where N is the normality of the ferrous solutions determined by titrating 20 mls of K 2  Cr 2  O 7  solution as a blank. The multiplication factor of 0.2143 is broken down as follows: ##EQU2## where 12/4000 is the millequivalent weight of carbon for the oxidation reaction, the conversion of organics in the oxidation reaction is 89% as reported in the U.S. Dept. of Argiculture Handbook referred to above, and 80.3 is the precent carbon in the butumen sample. It should be noted that the carbon content of bitumen is 80.3% as reflected in the above equation, but the carbon content of soil organic matter is less, being ##EQU3## which factor is used in the calculation of the referenced method. 
     The percent observed bitumen is calculated by subtracting the percent adsorbed organics from FIG. 3 (calculated from the methylene blue procedure) from the percent organics (from chromic acid oxidation) calculated as follows: 
     
         % adsorbed organics=(% clay minerals)×0.0234 
    
     
         % observed bitumen=% organics-% absorbed organics 
    
     Results 
     Table 1 gives the data using Ferroin as indicator and compares the percent bitumen to the percent bitumen determined by the conventional solvent extraction (CAM) method. An average for the ratio of the percent bitumen with the titration to the percent bitumen by the CAM method was found to be 0.9571±0.0762 for the Ferroin titration described above. 
     
                                           TABLE 1__________________________________________________________________________COMPARISON OF BITUMEN DETERMINATIONS                                  % Clay                                  Minerals   Sample       Volume 1N             Volume 0.506N                      Volume of   from  %           % BitumenSample  Wt. K.sub.2 Cr.sub.2 O.sub.7             Fe(NH.sub.4).sub.2 (SO.sub.4).sub.2                      K.sub.2 Cr.sub.2 O.sub.7                                  Methylene                                        Organics    By CAM#       (g) (mls) (mls)    (mls) % Organics                                  Blue  Absorbed                                              % Bitumen                                                    Method__________________________________________________________________________1       1.72911       100   35.29    82.35 10.20 14.044                                        0.3286                                              9.87  11.2   0.13968       20    25.86    7.07  10.84             10.512       1.38796       100   65.20    67.40 10.41 14.756                                        0.3453                                              10.06 10.3   0.14885       20    25.55    7.22  10.40             10.053       1.47134       100   74.70    62.65 9.12  17.222                                        0.4030                                              8.72  9.3   0.14668       20    27.25    6.37  9.31              8.914       0.22638       10    4.56     7.72  7.31  18.301                                        0.428 6.88  8.25       0.33558       100   173.63   13.18 8.42  19.855                                        0.465 7.96  8.56       0.63076       100   144.13   27.93 9.49  18.136                                        0.424 9.07  8.1   0.14597       10    8.55     5.72  8.41              7.997       0.98705       100   114.04   42.98 9.33  17.992                                        0.421 8.91  8.2   0.17898       10    5.75     7.12  8.53              8.118       1.04207       100   101.66   49.17 10.11 17.663                                        0.4133                                              9.70  9.3   0.18529       20    23.16    8.42  9.74              9.339       1.92485       100   23.74    88.13 9.81  20.559                                        0.4811                                              9.33  10.7   0.23531       20    16.05    11.98 10.91             10.4310      0.35956       20    5.92     17.04 10.16 17.399                                        0.4071                                              9.75  10.311      0.37313       20    3.87     18.06 10.37 15.497                                        0.363 10.01 11.4C-10    3.40715       10    17.30    0.639 0.0402                                  2.03  0.0475                                              0.0795                                                    0.0065TailingsDebitu- 0.46216       10    13.20    2.86  1.325 22.58 0.5283                                              0.797 1.30menizedSludge Sample__________________________________________________________________________ 
    
     As can be seen from the data in the table the percent bitumen are determined by the method of this invention compares very favorably in sample numbers 1 through 11. In the last two runs it it believed that the very low amount of bitumen in the samples presented as yet unrecognized experimental difficulties which adversely affected the results. Nevertheless, the process of the invention does enable a rapid analysis of bitumen content in tar sands, or tailings and sludge therefrom and thus represents a significant advance in the art.