Abstract:
A process for recovering carbonaceous organic material from a subterranean formation containing carbonaceous organic material which comprises introducing into the formation a cyclohexene or cyclohexadiene, maintaining contact between the carbonaceous organic material and the cyclohexene or cyclohexadiene for a time and at a temperature sufficient to obtain carbonaceous organic material of reduced viscosity and then recovering carbonaceous organic material of reduced viscosity.

Description:
This application is a continuation-in-part application of our U.S. patent application Ser. No. 927,865, filed July 25, 1978, now abandoned, for Process for Recovering Carbonaceous Organic Material From A Subterranean Formation. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to a process for recovering carbonaceous organic material from a subterranean formation containing said carbonaceous organic material which comprises introducing into said formation a cyclohexene or a cyclohexadiene, maintaining contact between said carbonaceous organic material and said cyclohexene or a cyclohexadiene for a time and at a temperature sufficient to obtain carbonaceous organic material of reduced viscosity and then recovering carbonaceous organic material of reduced viscosity. 
     2. Description of the Prior Art 
     It is well known that there exist throughout the world subterranean formations containing carbonaceous organic materials that are potentially recoverable by conventional insitu techniques. However, because of the lack of sufficient mobility of some of these carbonaceous organic materials, for example bitumen in tar sands, heavy, viscous crude oils, etc., at formation temperatures and pressures, conventional recovery techniques employed heretofor for substantially complete recovery of these carbonaceous materials have not been completely satisfactory, because they have not been economically and/or technically feasible. In some cases the recovery of carbonaceous materials that lack sufficient mobility in subterranean formation for feasible economic and/or technical recovery has necessitated the removal of the carbonaceous material and its associated inorganic materials from the subterranean formation to the surface for contact with solvent at elevated temperatures, as for example, U.S. Pat. Nos. 2,772,209 and 2,847,306 to Stewart et al. 
     SUMMARY OF THE INVENTION 
     We have discovered a process for recovering carbonaceous organic material from a subterranean formation containing said carbonaceous organic material which comprises introducing into said formation a cycloolefinic compound selected from the group consisting of a cyclohexene and a cyclohexadiene, maintaining contact between said carbonaceous organic material and said cycloolefinic compound for a time and at a temperature sufficient to obtain carbonaceous organic material of reduced viscosity and then recovering carbonaceous organic material of reduced viscosity. 
     Cyclohexenes that can be used in the process claimed herein can be defined by the following formula: ##STR1## wherein R 1  and R 2 , the same or different, can be hydrogen, an alkyl having from one to five carbon atoms, preferably one to two carbon atoms, a cycloalkyl having five carbon atoms, hydroxyl or a carbinol having from one to two carbon atoms, preferably one carbon atom; R 3  can be the same as R 1  and R 2 , provided that at least one of said R 3  is hydrogen and the total number of carbon atoms in the molecule is in the range of six to eleven, preferably six to eight. 
     Cyclohexadienes that can be used in the process claimed herein can be defined by the following formulae: ##STR2## wherein R 1 , R 2  and R 3  are as defined above and the total number of carbon atoms in the molecule is in the range of six to eleven, preferably six to eight. 
     Examples of cyclohexenes and cyclohexadienes that can be used herein include cyclohexene, 1-methylcyclohexene, 4-methylcyclohexene, 1,4-dimethylcyclohexene, 1-ethylcyclohexene, 1-propylcyclohexene, 1-n-pentylcyclohexene, 1-cyclopentylcyclohexene, 5-methyl-1-hydroxyl-2-cyclohexene, 1-carbinol-3-cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-methyl-1,3-cyclohexadiene, etc. Cyclohexenes or the cyclohexadienes need not be used in their pure form but can be used in dilution with any stream containing any of the same, as, for example, coker naphtha stream containing from about five to about 20 weight percent of any of these compounds. Coker naphtha can be obtained, for example, by any of the conventional coking processes wherein the residual portion of any petroleum, bitumen, etc., boiling at a temperature above about 425° C. is subjected to a temperature above about 435° C. and a pressure of about 35 pounds per square inch gauge (0.2 MPa) to obtain coke, gas and a liquid product. From the latter there is obtained a product, referred to as coker naphtha, having a boiling range, at standard temperature and pressure, of about 40° to about 255° C. 
     In carrying out the process of this invention the first step involves injecting the cyclohexene(s) and/or cyclohexadiene(s), as defined above, into a well in communication with a subterranean formation containing the carbonaceous organic material sought to be recovered. In order to carry out the process defined herein the formation in contact with the cyclohexene(s) and/or cyclohexadiene(s) must be at a temperature in the range of about 100° to about 450° C., or even higher, preferably about 135° to about 325° C., a pressure in the range of about 50 to about 4,000 pounds per square inch gauge (about 0.3 to about 27.5 MPa), preferably about 200 to about 2000 pounds per square inch gauge (about 1.3 to about 13.8 MPa) and for a period of about 0.5 hour to about 30 days or even higher, but preferably for about 24 hours to about seven days. 
     At the end of the operating period recovery of liquid product can be effected using any conventional procedure. Thus, for example, injection of the cyclohexenes or cyclohexadienes into the formation is terminated and liquid product is removed through the same injection well by standard depressurization and pumping techniques. Alternatively, the liquid product can be removed from one or more producing wells removed from, but in communication with, the injection well. Because the cyclohexenes or cyclohexadienes employed herein possess relatively low boiling points, and consequently relatively high vapor pressures, these materials possess high miscibility with the carbonaceous organic material and associated water, thereby increasing total formation pressure and enhancing fluid movement in the formation. 
     The products issuing from the formation of an emulsion will contain primarily water, gas and organic components. These components can be separated from each other by any conventional techniques, for example, stripping, settling and distillation. Because of the presence of the cyclohexenes or the cyclohexadienes in the emulsion, we have observed that the breaking and separation of the emulsion is more readily achieved than if cyclohexenes or cyclohexadienes were not present. 
     If the formation temperature naturally does not fall within the temperature range defined above, the temperature of the formation can be raised to the desired level by any suitable means, for example, by steam or combustion techniques. 
     In cases wherein steam is injected into the formation for the purpose of heating the carbonaceous organic material to the desired level and/or to provide a driving force to increase the mobility of carbonaceous organic material, it can be introduced into the formation prior to injection of the cyclohexenes or the cyclohexadienes into the formation, in conjunction with the cyclohexenes or the cyclohexadienes or after injection of cyclohexenes or the cyclohexadienes. In addition any cyclic arrangement of the above injections can be used. The relative amounts of steam and cyclohexenes or the cyclohexadienes used in the above can be infinitely varied to obtain the desired objectives. Under the conditions of operation defined hereinabove, the steam and the cyclohexenes or the cyclohexadienes are substantially miscible in each other. 
     As a result of treating the carbonaceous organic material in the subterranean formation with the cyclohexenes or the cyclohexadienes, as defined above, a carbonaceous organic material of reduced viscosity is obtained. In addition we have found that the weight percents of asphaltenes and of sulfur in the recovered carbonaceous organic material are lower than the weight percents of asphaltenes and of sulfur of the untreated carbonaceous organic material. While we are not sure as to the mechanism occurring in the defined treatment of the carbonaceous organic material with cyclohexenes or cyclohexadienes, we can postualte that perhaps hydrogen transfer may occur between the carbonaceous organic material and the cyclohexenes or cyclohexadienes, possibly resulting in depolymerization and desulfurization of the carbonaceous organic material and reducing the asphaltene content thereof; reaction may occur between the cyclohexenes or the cyclohexadienes and the carbonaceous organic material, resulting in a carbonaceous organic material of reduced viscosity. Some other mechanism may be primarily responsible for the reduction in viscosity of the carbonaceous organic material; or some combination of two or more of the above may occur. In any event the removal of carbonaceous organic material from a subterranean formation is facilitated by following the dictates of the process claimed herein and a product carbonaceous organic material is recovered having enhanced properties as to viscosity and to the relative amounts of asphaltenes and sulfur present. 
    
    
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     EXAMPLE I 
     An insulated steel cell having a length of 10 inches (25.4 centimeters) and a diameter of one inch (2.5 centimeters) was packed with core samples of rich tar sands containing from about 10 to about 16 weight percent of bitumen from the Cold Lake or Wabasca fields in Alberta, Canada. The raw tar sands were packed into the steel cell to simulate the porosity of the in-situ deposits. In each of the two cells used the porosity was about 50 percent and the pore volume about 80 cubic centimeters. Either cyclohexene or coker naphtha was passed upwardly through the externally-heated insulated steel cells using a flow rate of 645 milliliters per hour and at selected temperatures, pressures and flow rates to simulate the movement of fluid through a formation. Upon completion of the runs, the resulting bitumen product was recovered and analyzed. In each case all of the bitumen was recovered from the core samples. The results obtained are set forth in Table I. 
     
                                           TABLE I__________________________________________________________________________                  Cell Pres-                  sure, Pounds                         Duration   Cyclohexene           Cell   Per Square                         of   Weight                                   Weight ViscosityRun   Core or      Temperature,                  Inch Gauge                         Run, Percent                                   Percent                                          cps atNo.   Source   Coker Naphtha           °C.                  (MPa)  Hours                              Sulfur                                   Asphaltenes*                                          93° C.**__________________________________________________________________________1  Cold Cyclohexene            25    14.7 (0.1)                         1.0  4.5  23     125   Lake2  Wabasca   Cyclohexene            25    14.7 (0.1)                         1.0  5.5  17     9553  Cold Coker   135    14.7 (0.1)                         1.0  4.4  18     125   Lake Naphtha4  Cold Coker   150    600 (4.1)                         24   3.5  5.2    NT***   Lake Naphtha5  Cold Coker   150    600 (4.1)                         100  3.5  5.2    110   Lake Naphtha6  Cold Coker   150    1100 (7.6)                         24   3.4  4.4    NT***   Lake Naphtha7  Cold Coker   150    1100 (7.6)                         100  3.4  4.4    101   Lake Naphtha8  Cold Coker   200    600 (4.1)                         24   3.4  4.6    NT***   Lake Naphtha9  Cold Coker   250    600 (4.1)                         100  3.3  4.6    82   Lake Naphtha10 Cold Coker   300    600 (4.1)                         100  3.0  4.0    37   Lake Naphtha11 Cold Coker   300    1100 (7.6)                         100  2.6  3.0    9   Lake Naphtha12 Wabasca   Coker   250    400 (2.7)                         90   3.3  3.0    50   Naphtha13 Wabasca   Cyclohexene           250    410 (2.8)                         90   3.4  4.0    5014 Wabasca   Cyclohexene           250    410 (2.8)                         4    5.5  12.0   NT***__________________________________________________________________________ *n-pentane insolubles **Viscosity determined on an LVT Brookfield Viscometer using a shear rate of 15.8 inverse seconds. ***Not taken 
    
     Runs Nos. 1 and 2 were similarly carried out using benzene, toluene, tetrahydrofuran and chloroform. The product analysis was found to be the same in each instance. Accordingly, the product in Runs Nos. 1 and 2 is identical to the in-place bitumen in the tar sands. 
     The coker naphtha employed in the above runs was obtained as a result of a delayed coking operation from the Gulf Oil Corporation, Port Arthur, Tex., refinery and was analyzed as follows: 
     
                       TABLE II______________________________________Boiling Range (ASTM D-86):            40°-250° (C.sub.5 -C.sub.11)F1A Analysis (ASTM D-1319)and Mass Spectrometry:            52 Weight Percent Saturates            12 Weight Percent Aromatics            12 Weight Percent Cyclic              Olefins (Cyclohexenes and              Cyclohexadienes)            24 Weight Percent Aliphatic              Olefins______________________________________ 
    
     The data in Table II clearly illustrate the advantages of operation in accordance with the process defined and claimed herein. Although in Run No. 3 there was a reasonable drop in asphaltene content in the product, the contact was not of sufficient duration to effect any noticeable reduction in viscosity of the bitumen. We believe that had longer contact time been in effect in Run No. 3 a noticeable reduction in viscosity would have taken place. Increasing the temperature, pressure and contact in Run No. 4 resulted in a product having a lower sulfur content and a significantly lower asphaltene content. Simply increasing contact time in Run No. 5 produced no further decrease in sulfur and asphaltene content. However, note that the viscosity of the bitumen product was significantly lower than the in-place bitumen. It is believed that the drop in weight percent asphaltenes in the treated product is a result of the reaction between the bitumen and the cyclic olefins, resulting in a product of reduced viscosity. Had viscosity measurement been made of the product in Run No. 4, it would therefore have been expected that its viscosity would have been about the same as those of Run No. 5. Runs Nos. 6 to 12 additionally show the effect in varying the temperature, pressure and contact time in the process claimed herein. Best results appear to be obtained at elevated temperatures and pressures, as evidenced by Run No. 11 wherein the sulfur, asphaltenes and viscosity all reach a minimum. A comparison of Runs Nos. 13 and 14 with Run No. 12 clearly illustrate that pure cyclohexenes or cyclohexadienes are not needed, since the results obtained in each case are essentially the same. 
     EXAMPLE II 
     An insulated steel cell having a length of 48 inches (122 centimeters) and a diameter of 11/2 inches (3.8 centimeters) was packed with core samples from the same Cold Lake field as in Example I. The pore volume and porosity were essentially the same. In Run No. 1, 400 milliliters per hour of steam at a temperature of 300° C. and a pressure of 600 pounds per square inch gauge (2.0 MPa) was passed upwardly through the cell (thereby maintaining the temperature of the cell at 300° C. and the pressure at 600 pounds per square inch gauge (4.1 MPa)) over a period of five hours, at the end of which time no further bitumen appeared to be present in the product line. Run No. 2 was similar to Run No. 1, except that the steam was at a pressure of 1100 pounds per square inch gauge (7.6 MPa). Run No. 3 was similar to Run No. 1 except that after adding steam to the cell for five hours 40 milliliters per hour of the same coker naphtha used in Example I was commingled with the steam. This was continued for two hours. At the end of this period no further bitumen appeared in the product. Run No. 4 was similar to Run No. 3 except that the steam was at a pressure of 1100 pounds per square inch gauge (7.6 MPa). In Run No. 5 steam was injected into the cell for a period of five hours as in Run No. 1, at which time steam flow was stopped, and coker naphtha was injected into the cell at a rate of 400 milliliters per hour for 30 minutes. Coker naphtha flow was then stopped and steam was again injected as at the beginning for one hour. No further bitumen appeared in the product. Run No. 6 was a repeat of Run No. 5 but at 1100 pounds per square inch gauge (7.6 MPa). Run No. 7 was a repeat of Run No. 5 except that after the last steam injection a second slug of coker naphtha alone was injected at 400 milliliters per hour for 30 minutes, followed by an additional slug of steam alone as previously used for 30 minutes. No further bitumen appeared in the product. Run No. 8 was the same as Run No. 7 except that the pressure was maintained at 1100 pounds per square inch gauge (7.6 MPa). The resulting bitumen product obtained in each of these runs was analyzed. The data are set forth below in Table III. 
     
                       TABLE III______________________________________                              WeightRun  Weight Percent    Weight Percent                              PercentNo.  Bitumen Removed from Cell                  Asphaltenes Sulfur______________________________________1    39                23          4.42    46                23          4.43    99                3.1         3.04    99                3.1         3.05    77                4.0         3.56    83                4.0         3.57    91                4.0         3.58    97                4.0         3.5______________________________________ 
    
     Material balances were made for Runs Nos. 7 and 8 in Table III. The results are set forth below in Table IV. 
     
                       TABLE IV______________________________________Run No. 7          Introduced          Into System  Recovered______________________________________Water, cc.      2493         2384Coker Naphtha, cc           576          575Bitumen In Core, gm.            65.5         60.0Composition of Bitumen          18 Wt. % Asphal-                       4.4 Wt. % Asphal-          tenes        tenes          4.4 Wt. % Sulfur                       3.5 Wt. % Sulfur          210 Cps Vis- 74 Cps Vis-          cosity       cosity          At 200° F.                       At 200° F.          (93.3° C.)                       (93.3° C.)______________________________________Run No. 8          Introduced          Into System  Recovered______________________________________Water, cc.      2490         2490Coker Naphtha, cc.           391          391Bitumen In Core, gm.            68.8         68.0Composition of Bitumen          18 Wt. % Asphal-                       4.0 Wt. % Asphal-          tenes        tenes          4.4 Wt. % Sulfur                       3.5 Wt. % Sulfur          210 Cps Vis- 66 Cps Vis-          cosity       cosity          At 200° F.                       At 200° F.          (93.3° C.)                       (93.3° C.)______________________________________ 
    
     In each of Runs Nos. 7 and 8 above, all of the water, coker naphtha and bitumen in the system were accounted for; the slight amounts of water and bitumen that were not recovered were found to be in the core samples. 
     The data in Tables I and III show that whether or not cyclohexene is injected alone, coinjected with steam or cyclic injection of cyclohexene and steam are used, the same desired reductions in asphaltene and sulfur in the bitumen product are obtained. In addition, it can be seen that operation in accordance with the process claimed herein results in significantly increased bitumen recovery. 
     Obviously, many modifications and variations of the invention, as hereinabove set forth, can be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.