Patent Publication Number: US-2021188684-A1

Title: Method for treatment of oil-based sludge using thermal desorption

Description:
The present invention is directed to a method for treating oil-based sludge by thermal desorption, characterized in that it comprises a stage for conditioning oil-based sludge in which rice husk is added to form a homogeneous mixture before entering the rotary kiln of the Thermal Desorption Unit (TDU). Specifically, the method of the present invention is an indirect thermal high temperature desorption method, and the steps that constitute said method are:
         (a) Conditioning the oil-based sludge by adding rice husk;   (b) Putting the mixture in a rotary kiln that transfers the heat from the combustion of a fossil fuel to the mixture;   (c) Heating the mixture to generate desorption of the water and the organic components from the solid matrix;   (d) Passing the vapors generated in stage (c) through condensers that, through heat exchange, return said vapors to liquid state;   (e) Transporting the liquid to oil and water recovery tanks; and   (f) Transferring the treated solid to a pit.       

     In an alternative embodiment of the invention, the method for treating oil-based sludge by thermal desorption comprises a stage prior to the addition of the rice husk, comprising initial characterization of the oil-base sludge by a retort process. 
     The method of the present invention is characterized in that the volumetric increase of the oil-based sludge once the rice husk is added is 5% to 35% of the initial volume of oil-base sludge. 
     In one embodiment of the invention the ratio of oil-based sludge and rice husk is 1:1 to 1:1.5. Preferably, said ratio of oil-based sludge to rice husk is 1:1 to 1:1.3 and ideally, said ratio of oil-based sludge to rice husk is 1:1.2. 
     The method of the present invention, where heating that occurs in the stage (c) is carried out at temperatures ranging from 500° C. to 700° C. Additionally, the method of the present invention includes a step of cleaning the oven at the end of the process, which includes a decrease in the temperature between 250° C. and 300° C., followed by a controlled increase in temperatures between 550° C. and 600° C., and of the rotation of the unit to produce the expansion and contraction of the oven body, which will fracture and detach the crusts that form on the oven walls. 
     The detail of the process that determined that the conditioning prior to desorption thermal oil-based sludge had to be carried out with rice husk is discussed below in Example 1. Likewise, Example 2 discusses a preferred embodiment to put the invention into practice, when the method is applied on an industrial scale. None of the examples presented below constitutes a limitation for the present invention. 
     EXAMPLE 1 
     Comparative Evaluation Of Different Treatment Methods for Oil-Based Sludge by Thermal Desorption 
     To evaluate the results achieved with the method of the present invention, 13,000 barrels of oil-based drilling sludge from the drilling of oil wells in the foothills of the plains were treated and finally disposed, making use of the high temperature indirect thermal desorption process in which the material to be treated was previously conditioned with different filler materials, such as calcium oxide, sand, native soil and rice husk. 
     The results obtained related to the processing rate, percentage of oil recovery and volumetric increase with respect to the initial volume of the fluid are shown below. The selection of filler materials or excipients used for the sludge conditioning comprised a prior analysis of some general characteristics, as well as the advantages and disadvantages that it would have on the desorption process. 
                     TABLE 1                  Prior analysis of possible advantages and disadvantages of filler materials                         Material   Potential advantages   Potential disadvantages               Calcium    Abundant and easy to obtain   Increase in cost per unit and       Oxide       transport           Reduces humidity due to the   May generate cake inside           following chemical reaction:   oven               May develop incrustation in               oven               Thin       River    Ideal particle size for thermal   Increase in cost per unit and       sand   desorption   transport           Abundant and easy to obtain   High weight           Potential reuse   Humidity       Native    Appropriate particle size for   High weight       soil   thermal desorption               Abundant and easy to obtain   Soil contamination               Humidity       Rice husk   Ideal particle size for    Increase in cost per unit and           thermal desorption   transport           Abundant and easy to obtain   Potential thermal degradation           Organic   in operating temperatures           Los weight               Low cost due to being               considered an agro-industrial               residue                    
Then, the methodology described below was applied to determine what could be the conditioning method for oil-base sludge which allowed to overcome the technical problem raised in the present application. The following steps were performed:
     1. Initial characterization of the oil-based sludge by a retort process;   2. Mixtures of oil-based sludge with calcium oxide, river sand, native soil, rice husk in proportions (1:1), (1:1.5) and (1:1.2);   3. Qualitative evaluation of the physical properties of the resulting mixture;   4. Characterization of the resulting mixtures by the retort process;   5. Preparation of pilot mixture for trial on an industrial scale; and   6. Evaluation of variables and performance indicators of the thermal desorption.   

     The oil-base sludge was initially characterized by triplicate analysis of a composite sample taken from the storage pool in different points and at different depths using a vacuum truck. The sampling methodology used sought to minimize possible variations in the composition, due to sedimentation of the sludge densifiers. The results of the characterization and composition of the base sludge are shown in Table 2. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Characterization of oil-based sludge by a retort method and sludge balance  
               
            
           
           
               
               
            
               
                   
                 Results 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Sub-sample 
                 Sub-sample 
                 Sub-sample 
                 Sub-sample 
                 Sub-sample 
               
               
                 Parameter 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 % v/v Oil 
                 60 
                 70 
                 54 
                 61 
                 8.0 
               
               
                 % v/v Water 
                 18 
                 14 
                 22 
                 18 
                 4.0 
               
               
                 % v/v Solid 
                 22 
                 16 
                 24 
                 21 
                 4.2 
               
               
                 Density (ppg) 
                 12.3 
                 11.2 
                 11.8 
                 11.8 
                 0.6 
               
               
                   
               
            
           
         
       
     
     The formulation of the mixtures with calcium oxide, sand, native soil and rice husk analyzed corresponds to the percentages shown in Table 3. Based on physical appearance, a qualitative description of the appearance and/or texture of the resulting mixture, in order to discard those mixtures that could represent difficulties for the controlled entry of the material into the oven through the endless screw due to its fluidity. Likewise, the volumetric increase was identified with respect to the original residue due to the contribution of material. 
                     TABLE 3                  Oil-based sludge and filler material mixtures                                             Sludge                           volume   Sludge/Deposition   Quality   Volumetric       Material   Mixture   (mL)   ratio   description   increase                                             Calcium   1   300   1:1   Fluid   30%       Oxide   2         1:1.5   Semi-pasty   45%           3       1:2   Pasty   100%        River sand   4       1:1   Fluid   50%           5         1:1.5   Semi-pasty   80%           6       1:2   Pasty   110%        Native soil   7       1:1   Fluid   50%           8         1:1.5   Fluid   70%           9       1:2   Semi-pasty   100%        Rice husk   10       1:1   Semi-pasty   10%           11         1:1.5   Pasty   25%           12       1:2   Pasty   35%                    
Of the mixtures indicated in Table 3, three were selected that gave results qualitatively appropriate to carry out thermal desorption according to the principles of the process (Mix 2, 11 and 12). However, the volumetric increase acceptable was determined at a maximum 35% to have economic feasibility, limiting the possible options to mixtures 11 and 12 of oil-base sludge with rice husk. The comparison between the physical appearance between original residue and residue mixed with rice husk is shown in  FIG. 1 .
 
     Taking into account the qualitative criteria, mixtures 11 and 12 were characterized by the retort process in order to identify reduction in the composition of liquids in percentage volume/volume due to dilution effect. The results are shown in Table 4. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Comparative retort analysis of mixtures 11 and 12 with oil-based sludge 
               
            
           
           
               
               
            
               
                   
                 Results 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 Mixture 
                 Avg. Oil-based 
               
               
                 Parameter 
                 Mixture 11 
                 12 
                 Sludge 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 % v/v Oil 
                 44 
                 40 
                 61 
               
               
                 % v/v Water 
                 18 
                 20 
                 18 
               
               
                 % v/v Solid 
                 38 
                 40 
                 21 
               
               
                 Density (ppg) 
                 12.1 
                 12.3 
                 11.8 
               
               
                   
               
            
           
         
       
     
     According to the results of Table 4, it was observed that, due to the volumetric increase by the addition of filler material, the concentration of the liquid components of the sludge in the mixtures was reduced. This effect is appropriate for minimizing heat transfer problems due to the design capacity of the condensers and improving the recovery of oil associated with the residue. Also qualitatively evaluated was the behavior of the solid material in the glass of the retort and possible migration to filters, in order to try to predict cake formations in the oven and thin solids that could be washed away with the steam flow to the TDU condensers. Phase separation in analysis of sludge mixture with rice husk are observed in  FIG. 2 . 
     After the analysis of the mixtures, no cake formation was observed in the glass, contrary to what happened in the analysis of the sludge with calcium oxide. The rice husk did not suffer thermal degradation and the migration of thin solids towards the filters was not considerable. 
     EXAMPLE 2 
     Evaluation of the Method of the Present Invention at Scale Industrial 
     Using laboratory scale works as a reference, 8 potholes of mixture of oil-based sludge and rice husk in proportions (1:1.5) and (1:2) in the feed catch tanks of the thermal desorption unit, for scaling and evaluation at an industrial level of sludge treatment. Preparation is schematized in  FIG. 3 . 
     Industrial-scale tests were carried out for 8 days (24-hour operation), in order to preliminarily determine the average treatment rate of the TDU, volumetric expansion of the residue (Cex. v), as well as the stability in the oven temperatures. During the test days, the appropriate relationship for oil-based sludge and rice husk was set at 1:1.2, resulting in a volumetric expansion coefficient of 1.2 defined according to Equation 1. 
     
       
         
           
             
               
                 
                   
                     C 
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                     e 
                      
                     
                       x 
                       . 
                       v 
                     
                   
                   = 
                   
                     
                       Mix 
                        
                       
                           
                       
                        
                       Volume 
                        
                       
                           
                       
                        
                       
                         ( 
                         Bbl 
                         ) 
                       
                     
                     
                       Sludge 
                        
                       
                           
                       
                        
                       Volume 
                        
                       
                           
                       
                        
                       
                         ( 
                         Bbl 
                         ) 
                       
                     
                   
                 
               
               
                 
                   Equation 
                    
                   
                       
                   
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                   1 
                 
               
             
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Data collected during scaling days and TDU testing 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                   
                 Treatment 
                 Oven 
                   
                   
               
               
                   
                 Mixture 
                   
                 (sludge 
                 temperature 
                 Oven 
                 % Initial 
               
               
                 Day 
                 ratio 
                 Cev 
                 m3/day) 
                 range (° C.) 
                 stability 
                 Hydrocarbons 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 1:1.5 
                 1.1  
                 24.2 
                 461-683 
                 Unstable 
                 4 
               
               
                 2 
                 1:1.5 
                 1.1  
                 23.5 
                 644-700 
                 Stable 
                 2 
               
               
                 3 
                 1:1.5 
                 1:15 
                 25.4 
                 487-778 
                 Unstable 
                 6 
               
               
                 4 
                 1:1.5 
                 1.1  
                 21.5 
                 459-750 
                 Unstable 
                 3 
               
               
                 5 
                 1:2   
                 1.23 
                 30.7 
                 550-600 
                 Stable 
                 1 
               
               
                 6 
                 1:2   
                 1.19 
                 27.8 
                 540-610 
                 Stable 
                 0 
               
               
                 7 
                 1:2   
                 1.2  
                 29.6 
                 545-612 
                 Stable 
                 &lt;1 
               
               
                 8 
                 1:1.5 
                 1.21 
                 32 
                 535-602 
                 Stable 
                 &lt;1 
               
               
                   
               
            
           
         
       
     
     It was determined that the 1:1.2 mixing ratio between sludge and rice husk allowed to keep the oven of the thermal desorption unit stable with estimated fluctuations of no more than 50° C. (see  FIGS. 4 and 5 ). Under stable conditions, just enough heat energy is supplied to avoid overheating of the vapors generated in the oven and guarantee the complete removal of the contaminant from the solid matrix to levels lower or equal to 1% hydrocarbons. With the mixtures corresponding to the relation 1:1.5, there were difficulties in keeping the feeding rate constant with the endless screw due to the texture of the material. 
     With the results obtained during the scaling tests, a preparation protocol for oil-based sludge and rice husk mixtures, where the volume of sludge to be deposited in the catch tank was defined, the exact dosage amount of rice husk, the density and the estimated volumetric composition of the resulting mixture to minimize effects on stability and homogeneity of the furnace, thus achieving reproducible results later during the days of operation. 
     A relevant fact that became evident along the way was the formation of rings or refractory material crusts inside the oven after 15 continuous days of operation. An atomic absorption analysis of a sample revealed that the material adhered was constituted mainly by Barium, one of the components of the oil-based sludge. Contrary to what was observed in laboratory-scale tests, where no adherence of the material to the retort cup was evidenced, it was evident in the industrial process. The main unwanted effect of the generation of these crusts or cake in the oven, is the decrease in heat transfer from the combustion chambers towards the material being treated, causing the contaminant not to be eliminated completely from the solid matrix, breaching environmental regulations. Th problem was resolved, implementing oven cleaning routines on the fly, through the controlled decrease and increase of temperatures, causing the expansion and contraction of the oven body, in ranges that do not represent metal deformations. As a result, the scabs fractured and ended detaching with the help of unit rotation, restoring efficiency in heat transfer, as evidenced in  FIG. 6 . 
     Table 6 presents the data obtained from the thermal desorption process during a typical month of operation, treating oil-base sludge: 
                                                        Mixture       Treatment   Initial characterization   Oil Balance (m3)                                                 Date   volume (m3)   Cex · v   volume (m3)   % Oil   % Water   % Solid   Expected   Recovered                                                         1 Oct. 2015   31.        .2     25.9   5     21           1  .     11.4       2 Oct. 2015   3  .1      .18   2  .9   5     20   24   16.7   11.1       3 Oct. 2015   31.2      .2   25.     5     25   19   14.     11.1       4 Oct. 2015   31.3      .       25.9   57   2     20   14.        .8       5 Oct. 2015   38.2      .22   31.     58   2     21   17.6   1  .         6 Oct. 2015   34.8      .23   28.     48   36   16   13.8      .8       7 Oct. 2015   34.8   1.1     28.     44           2     12.     0.0       8 Oct. 2015   38.        .2     31.     40   45   15   12.7   10.3       9 Oct. 2015   3  .4      .2   30.1   50   2     21   15.1   10.3       10 Oct. 2015   27.2      .2   22.4   40   24   36   8.     0.0       11 Oct. 2015        .        .18   1  .4   4     2     2     8.     4.3       12 Oct. 2015   31.0      .22   25.        4   21   2          .        .         13 Oct. 2015   30.8      .22   25.4   50   20   30   12.7   4.         14 Oct. 2015   3  .2   1.18   27.5   5     20   24   1  .4      .         1   Oct. 2015      8.     1.17   2  .3   5     1     2     1  .7      .         20 Oct. 2015      .0   1.1     4.     53   20   27   2.     0.0       21 Oct. 2015        .9   1.1     28.0   51.5   20   2  .     14.5      .2       22 Oct. 2015   30.2      .1     25.0   51   26   2        2.7   11.0       23 Oct. 2015   3  .        .17   29.     51   21   2     1  .     11.         24 Oct. 2015        .2      .19   27.3   49   21      0   1  .     11.1       25 Oct. 2015   31.     1.2        .2   5     21   26   14.0   7.         26 Oct. 2015   3  .        .2     2  .     47   20           1  .     4.         27 Oct. 2015   3  .9      .1     27.             2     24   14.        .0       28 Oct. 2015        .2      .1     27.     47           2     12.     7.         29 Oct. 2015        .        .2   28.0   51           20   14.     7.         30 Oct. 2015   34.7   1.19   28.     49           2     14.0      .7       31 Oct. 2015   34.0   1.2   28.1   51   27   2     14.        .1       TOTALES             1.19 Avg.        2   —   —   —                                                 % Oil Recovery                           indicates data missing or illegible when filed            
In the previous table it is observed that the average volumetric expansion coefficient (Cex. v) was 1.19, that is, 11 percentage points below the limit set (30%) economically to make the thermal desorption treatment viable. Likewise, the oil recovery determined by Equation 2 was 54%, that is, 4 percentage points above the goal (50%).
 
     
       
         
           
             
               
                 
                   % 
                    
                   
                       
                   
                    
                   Oil 
                    
                   
                       
                   
                    
                   Recovery 
                    
                   
                     = 
                     
                       
                         
                           Recovered 
                            
                           
                               
                           
                            
                           Oil 
                            
                           
                               
                           
                            
                           Volume 
                            
                           
                               
                           
                            
                           
                             ( 
                             Bbl 
                             ) 
                           
                         
                         
                           Sludge 
                            
                           
                               
                           
                            
                           Volume 
                            
                           
                               
                           
                            
                           
                             ( 
                             Bbl 
                             ) 
                           
                           * 
                           % 
                            
                           
                               
                           
                            
                           Oil 
                            
                           
                               
                           
                            
                           in 
                            
                           
                               
                           
                            
                           Sludge 
                         
                       
                       * 
                       1 
                        
                       0 
                        
                       0 
                     
                   
                 
               
               
                 
                   Equation 
                    
                   
                       
                   
                    
                   2 
                 
               
             
           
         
       
     
     In light of the results shown, it was concluded that the conditioning of oil-based sludge with rice husk in a ratio of 1:1.2 before entering the TDU provides technical and economic feasibility and acceptable cost-benefit ratio within the project performance indicators, since the mixture with rice husk showed the best performance and made sludge treatment possible on an industrial scale with effective rates of 28.6 m3/day, oil recovery of 54%, volumetric increase of 19% compared to the original volume and a consumption of fuel adjusted to historical TDU consumption from the economic point of view. 
    
    
     DESCRIPTION OF THE FIGURE 
     For a better understanding of the invention, the following figures are included: 
       FIG. 1 : Comparison of physical appearance between original residue and residue mixed with rice husk. 
       FIG. 2 : Phase separation in analysis of sludge mixture with rice husk. 
       FIG. 3 : Preparation of oil-based sludge and rice husk mixture to industrial scale 
       FIG. 4 : Stability results in oven temperatures of the TDU for days 1, 2, 3 and 4 of tests. 
       FIG. 5 : Stability results in oven temperatures of the TDU for days 5, 6, 7 and 8 of tests. 
       FIG. 6 : Photograph of the formation of crusts of refractory material inside from the TDU oven.