Enhanced steam extraction of in situ bitumen

Abstract

A process includes: (a) injecting a steam composition into a subterranean location containing bitumen, the steam composition containing an alkylene glycol ether and steam, wherein the alkylene glycol ether is other than a glycol ether amine; and (b) recovering bitumen from the subterranean location to above the ground.

Claims

1. A process comprising: (a) injecting a steam composition into a subterranean location containing bitumen, the steam composition comprising an alkylene glycol ether and steam; and (b) recovering at least a portion of the bitumen from the subterranean location to above ground; wherein the alkylene glycol ether is other than a glycol ether amine and wherein the alkylene glycol ether has the following chemical formula:
H(OR.sub.1).sub.nOR.sub.2 where R.sub.1 is an alkylene unit, OR.sub.1 is an alkylene glycol unit, R.sub.2 is an alkyl or aryl, OR.sub.2 is an alkyl ether component or aryl ether component and n is an integer that has a value in a range of one or more to ten or less, each alkylene unit has more than two and eight or fewer carbons and when the value of n is more than one, the R.sub.1 in each of the alkylene glycol units is the same or different.

2. The process of claim 1, further characterized by the alkylene glycol ether being present in the steam composition at a concentration of 0.01 weight percent or more and 10 weight percent or less based on combined alkylene glycol ether and steam weight.

3. The process of claim 2, further characterized by the alkylene glycol ether being present in the steam composition at a concentration of 0.1 weight percent or more and five weight percent or less based on combined alkylene glycol ether and steam weight.

4. The process of claim 1, further characterized by the alkylene glycol ether being selected from monoalkylene glycol ethers and dialkylene glycol ethers.

5. The process of claim 1, further characterized by the alkylene glycol ether being monoalkylene glycol ether.

6. The process of claim 1, further characterized by the steam composition being free from hydrocarbons when injecting the steam composition into the subterranean location during step (a).

7. The process of claim 1, where the process is a steam assisted gravity drainage process and the steam composition is injected into the ground through a first well and bitumen that is displaced from the ground is recovered to above ground through a second well.

8. The process of claim 1, the process further characterized by being free of disposing a liquid-phase solvent or alkaline water-based extraction liquid into a well.

9. The process of claim 1, wherein the process is free of glycol ether amine as an extraction aid.

10. The process of claim 1, wherein the steam composition comprises a blend of two or more different alkylene glycol ethers.

11. The process of claim 1, wherein the alkylene glycol ether forms an azeotrope with water.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 provides an illustration of a vessel used to determine bitumen extraction efficiency in Experiments 1-9.

DETAILED DESCRIPTION OF THE INVENTION

(2) “Multiple” means two or more. “And/or” means “and, or as an alternative”. All ranges include endpoints unless otherwise indicated.

(3) The process of the present invention requires injecting a steam composition through a well into a subterranean location containing bitumen. The subterranean location is desirably in or proximate to an oil sand deposit. Oil sand is also known as tar sands or bituminous sands. Oil sand is loose sand, or partially consolidated sandstone containing mixtures of sand, clay and water, that includes bitumen. Canada, Kazakhstan and Russia all contain large quantities of oil sand deposits. The process of the present invention extracts bitumen from other components of the oil sands in a subterranean location by injecting a steam composition into the subterranean oil sand deposit to increase the flowability of the bitumen, thereby enabling the bitumen to drain from the oil sand components and eventually be recovered by pumping above ground. The process of the present invention avoids first having to remove oil sand from underground in order to extract bitumen from the removed oil sand as is required in a strip mining process. Instead, the present invention extracts bitumen from oil sands in situ, that is, in the subterranean location of the oil sand.

(4) The steam composition of the present invention comprises both steam and alkylene glycol ether. The composition is desirably injected at a temperature and pressure sufficient to provide a steam composition at a temperature of 150° C. or higher, preferably 180° C. or higher and at the same time desirably a temperature of 300° C. or lower, preferably 260° C. or lower.

(5) The steam in the steam composition can be superheated steam, saturated steam, less than 100 percent quality steam or any combination thereof. “Superheated steam” is steam that is at a temperature above the vapor-liquid equilibrium point of water. “Saturated steam” is synonymous with 100 percent quality steam. The quality of steam is a characteristic of how much liquid water phase is present in the steam. 100 percent quality steam has zero percent liquid phase water present. “Less than 100 percent quality steam” has liquid water present. A steam composition that is less than 100 percent quality steam can include the resulting composition from feeding a steam feed and a liquid aqueous phase feed together (as is done, for example, in Examples 1-5 herein).

(6) The alkylene glycol ether is desirably volatile at the temperature, pressure and environment of the steam composition when injected into a well as described above. Preferably, the alkylene glycol ether forms an azeotrope with water in order to optimize efficiency in dispersion and transport in steam.

(7) In the broadest scope of the present invention, the alkylene glycol ether is not limited in composition except that is it other than a glycol ether amine. In general, the alkylene glycol ether has the following chemical formula:
H(OR.sub.1).sub.nOR.sub.2
Where: R.sub.1 is referred to herein as an alkylene unit or the simply the alkylene, OR.sub.1 is referred to as an alkylene glycol unit, and R.sub.2 is referred to as an alkyl or aryl and OR.sub.2 is an alkyl ether component or aryl ether component. R.sub.2 can be a pure alkyl, pure aryl or it can be a substituted alkyl or aryl comprising elements other than carbon and hydrogen. “Pure” in this description means consisting of only carbon and hydrogen. Typically, R.sub.2 consists of carbon and hydrogen atoms. Desirably, R.sub.2 is linear, or straight-chain, which means if there are more than two carbons the carbons are bound in sequential fashion to form a chain without branching.

(8) The value of n is an integer that is one or more. While in the broadest scope there is no known upper limit for n, it is desirable for n to be 10 or less, preferably 8 or less, still more preferably 6 or less, even more preferably 4 or less and can be 3 or less, even 2 or less and n can be one. When n is one, the compound is a monoalkylene glycol ether. When n is two, the compound is a dialkylene glycol ether. When n is three, the compound is a trialkylene glycol ether. When n is greater than one, the compound is broadly considered a polyalkylene oxide ether. R.sub.1 and R.sub.2 are carbon-containing moieties and preferably R.sub.1, R.sub.2 or both R.sub.1 and R.sub.2 consist of only carbon and hydrogen. When n is greater than one, R.sub.1 in each of the alkylene glycol units can be the same or different. If the alkylene glycol ether contains different alkylene units, then each of the alkylene units are consistent with requirements for alkylene units stated below and independently can adhere to the optional (for example, desirable or preferred) characteristics for alkylene units described below.

(9) Desirably, the alkylene glycol ether is selected from monoalkylene, dialkylene and trialkylene glycol ethers as opposed to polyalkylene glycol ethers having more than three alkylene glycol units. The shorter monoalkylene, dialkylene and trialkylene (especially the mono and dialkylene) glycol ethers tend to: (a) be more volatile and have better mobility with the steam; and (b) penetrate into oil sands more quickly and readily than larger polyalkylene glycol ethers.

(10) In addition to the preferences for number of alkylene glycol units, or as an alternative to the preferences for the number of alkylene glycol units, it is possible for the alkylene glycol unit to have more than two carbon atoms per alkylene unit. It has been surprisingly discovered that alkylenes longer than ethylene are effective for use in facilitating steam extraction of bitumen from oil sand in an in situ process. At the same time, it tends to be desirable for each alkylene unit to contain fewer than 8, preferably 6 or fewer and more preferably 5 or fewer carbons and typically 4 or fewer carbon atoms. Desirably, each alkylene unit contains three or four carbons, preferably three carbons.

(11) In addition to any one or both of the number of alkylene unit preferences and number of carbons per alkylene unit preferences, or as an alternative to either or both of those preferences, it is generally desirable for the entire alkylene glycol ether molecule to contain fewer than ten carbon atoms. When the alkylene glycol ether contains fewer than ten carbon atoms it is believed that the ethylene glycol ether tends to be both more volatile and exhibit greater mobility within the oil sands.

(12) Examples of desirable alkylene glycol ethers include those selected from a group consisting of ethylene glycol ether, propylene glycol ether and butylene glycol ether. Especially desirable are monoalkylene, dialkylene and trialkylene versions of ethylene glycol ether, propylene glycol ether and butylene glycol ether. The alkylene glycol ether can be selected from monoalkylene and dialkylene versions, or even just monoalkylene versions, of ethylene glycol ether, propylene glycol ether and butylene glycol ether. Surprisingly, the selected alkylene glycol ether can be the propylene glycol ether and/or butylene glycol ethers.

(13) Specific examples of suitable alkylene glycol ethers include any one or any combination of more than one of the following: propylene glycol n-butyl ether (such as DOWANOL™ PnB glycol ether, DOWANOL is a trademark of The Dow Chemical Company), dipropylene glycol methyl ether (such as DOWANOL DPM glycol ether), dipropylene glycol n-propyl ether (such as DOWANOL DPnP glycol ether), propylene glycol n-propyl ether (such as DOWANOL PnP glycol ether), dipropylene glycol n-butyl ether (such as DOWANOL DPnB glycol ether), ethylene glycol monohexyl ether (for example, Hexyl CELLOSOLVE™ solvent, CELLOSOLVE is a trademark of The Dow Chemical Company), ethylene glycol mono-n-propyl ether (such as propyl CELLOSOLVE Solvent), diethylene glycol monohexyl ether, ethylene glycol mono-n-propyl ether (such as Propyl CELLOSOLVE Solvent), diethylene glycol monohexyl ether (such as Hexyl CARBITOL™ Solvent, CARBITOL is a trademark of The Dow Chemical Company), diethylene glycol monobutyl ether (such as Butyl CARBITOL Solvent) and triethylene glycol monobutyl ether.

(14) The steam composition can contain one alkylene glycol ether or a mixture of more than one kind of alkylene glycol ether. Desirably, if the steam composition contains a mixture of more than one kind of alkylene glycol ether, more than one of the alkylene glycol ethers and preferably all of the alkylene glycol ethers are selected from those having the properties as described above for the alkylene glycol ether of the present invention.

(15) The amount of alkylene glycol ether required in the steam composition to achieve improvement in bitumen extraction over steam alone is surprisingly low. The steam composition can contain as little as 0.01 weight-percent (wt %) of alkylene glycol ether and still demonstrate an improvement in bitumen extraction over use to steam alone in the same process. Typically, the steam composition contains 0.05 wt % or more, more typically 0.1 wt % or more, more typically 0.2 wt % or more, and can contain 0.3 wt % or more, 0.4 wt % or more or 0.5 wt % or more alkylene glycol ether. At the same time, the steam composition can contain 25 wt % or less, yet preferably contains 10 wt % or less, more preferably 7 wt % or less, yet more preferably 5 wt % or less and can contain 4 wt % or less alkylene glycol ether. Excessive amounts of alkylene glycol ether cause the cost of the process to increase so lower concentrations of the alkylene glycol ether are desirable from a cost standpoint. The wt % of alkylene glycol ether is based on total combined weight of steam and alkylene glycol ether.

(16) Desirably, the steam composition is free of glycol ether amine. In general, the process of the present invention is desirably free of glycol ether amine as an extraction aid. Amines tend to be undesirably thermally unstable and can break down during the injection process they also tend to chemically bind to components in the process.

(17) The steam composition can be free from hydrocarbons when injecting the steam composition into a subterranean location. The process of the present invention can be free of injecting hydrocarbons in any manner, whether in a steam composition or otherwise, into a well. Use of hydrocarbons is unnecessary in the present invention. Moreover, hydrocarbons can be undesirable for reasons set forth in the Background section.

(18) It is also desirable for the process of the present invention to be free of injecting a liquid-phase solvent or an alkaline water-based extraction liquid into a well. These steps are unnecessary in the present invention and would unnecessarily add complexity the present extraction process.

(19) In its broadest scope, the present invention is independent from how to form the steam composition. For example, an aqueous solution of the alkylene glycol ether can be boiled to create the steam composition, alkylene glycol ether (neat or as an aqueous solution) can be introduced to steam, or any combination thereof.

(20) After injecting the steam composition into a subterranean location containing bitumen, the process further includes extracting bitumen from the subterranean location to above the ground. The steam composition serves to cause the bitumen to become flowable allowing it to be pumped from underground to above ground. The process of the present invention can take the form of a cyclic steam stimulation (CSS) process where bitumen is pumped up the same well that the steam composition is injected, a steam assisted gravity drainage (SAGD) where bitumen is pumped up a second well other than the well through which the steam composition is injected into the ground, or conceivable a combination of both CSS and SAGD type processes.

Examples 1 and 2

(21) Alkylene glycol ethers for use in the following examples can be made by ordinary means known to one of ordinary skill in the art by reacting the appropriate alcohol with the appropriate alkylene oxide in the presence of a suitable catalyst and then distilling the resulting mixture to obtain the alkylene glycol of interest. When commercially available, the commercial trade name is provided below.

(22) The examples use a set up similar to that illustrated in FIG. 1 to simulate steam assisted extraction of bitumen from oil sands. Provide a container 10 having lid 12 with entrance opening 14 defined there through and opposing bottom 16 with exit opening 18 defined there through. Within container 10 place the following in order: screen 20 over bottom 16 so as to cover exit opening 18, 100 grams of high-grade mined oil sand (from Alberta Innovates Technology Futures sample bank) 30 over screen 20, screen 22 covering oil sand 30, a layer of glass beads 40 covering screen 22, screen 24 covering glass beads 40 and spring 50 under compression and positioned between lid 12 and screen 24 so as to hold the contents of container 10 in place. Heater 60 is located around container 10 so as to heat the oil sand 30 to a steam saturation temperature during the experiment.

(23) To simulate oil recovery, inject steam, or steam composition depending on the example, into entrance opening 14 and maintain the injection pressure at 0.8 megaPascals (MPa) for one hour (stage 1) and then increase the pressure to 1.6 MPa for another hour (stage 2). Set heater 60 to the saturation temperature during each stage. Collect discharge from container 10 through exit opening 18.

(24) Inject a steam composition in to opening 14 by co-injecting two streams into opening 14. The first stream is steam injected at four milliliters per minute (liquid water equivalent volume). The second stream is 0.5 milliliters per minute of liquid water. For the examples of the present invention, the liquid water stream contains one wt % of an alkylene glycol ether as identified in Table 1 for a concentration of alkylene glycol ether of 0.1 wt % relative to a combination of steam and alkylene glycol ether weight.

(25) Determine percent bitumen recovery at two points in the process. Determine an Initial Weight-Percent Recovery based on the amount of oil in the discharge collected over the first 20 minutes of the process. Determine a Final Weight-Percent Recovery based on the amount of bitumen in the discharge collected over the full two-hour process. Determine the amount of bitumen extracted at each interval by toluene extraction of the discharge. The toluene extraction method includes mixing toluene with the discharge mixture, isolating the toluene layer, evaporating the toluene to isolate the extracted bitumen and then weighing the extracted bitumen. Determine the percent bitumen recovery for the two points in the process by dividing the weight of the extracted bitumen by the weight of the bitumen in the original oil sand material. Determine the weight of bitumen in the original oil sand by doing a toluene extraction of a sample of the original oil sand having a known weight. From the known weight of the oil sand sample and the weight of bitumen extracted in the toluene extraction the wt % bitumen in the oil sand is readily calculated by dividing the extracted bitumen weight by the known oil sand weight and multiplying by 100. This value can be used to determine how much bitumen was in the oil sand used in the experiments by first measuring the weight of the oil sand prior to injecting the steam or steam composition.

(26) Table 1 provides the results for a Reference that contains no alkylene glycol ether as well as Examples 1 and 2 that illustrate examples of the present invention where the steam composition contains 0.1 wt % of alkylene glycol ether.

(27) TABLE-US-00001 TABLE 1 Initial Wt % Final Wt % Sample Alkylene Glycol Ether Recovery Recovery Reference (none) 13 32 Example 1 Dipropylene glycol n-propyl 20 35 ether (DOWANOL DPnP) Example 2 Dipropylene glycol n-butyl 18 34 ether (DOWANOL DPnB)

(28) The data in Table 1 reveals that even at a concentration of 0.1 wt % in steam the yield of bitumen from a steam extraction of oil sand is noticeably increased by the presence of the alkylene glycol ether. The improvement evident from Table 1 data is expected to correlate to actual in situ steam extraction performance from subterranean oil sands.

Examples 3-7

(29) Carry out the process for another reference sample and Examples 3-7 using the same procedure as for Examples 1 and 2 (and the associated reference) except prepare the steam, or steam composition, in the following manner. Instead of injecting a steam stream and a liquid stream into container 10 to form the steam or steam composition, inject only a single stream of steam that already contains any alkylene glycol ether additives specified. Prepare the single stream of steam by generating steam from water (for the reference) or from an aqueous solution containing either 0.1 wt % or 0.4 wt % of the designated alkylene glycol ether (see Table 2) and injecting that generated steam into container 10. The identity of the alkylene glycol ethers for Examples 3-7 and the extraction results are provided in Table 2.

(30) The data in Table 2 reveals that at a concentration of 0.1 wt % or 0.4 wt % in steam the yield of bitumen from a steam extraction of oil sand is noticeably increased by the presence of the alkylene glycol ether. The improvement trends evident from Table 2 data is expected to correlate to actual in situ steam extraction performance from subterranean oil sands. That is, additives showing higher recovery percentages in this experiment than the reference are expected to show higher recovery percentages in an in situ subterranean steam extraction relative to a recovery process without the additive.

(31) TABLE-US-00002 TABLE 2 0.1 wt % Alkylene 0.4 wt % Alkylene Glycol Ether Glycol Ether Initial Final Initial Final Alkylene Wt % Wt % Wt % Wt % Glycol Recov- Recov- Recov- Recov- Sample Ether ery ery ery ery Reference (none) 13  36* 13 36 Example 3 dipropylene 17 38 20 41 glycol n- propyl ether (DOWANOL DPnP) Example 4 dipropylene 14 33 15 37 glycol n- butyl ether (DOWANOL DPnB) Example 5 Dipropylene 12 38 16 44 glycol methyl ether (DOWANOL DPM) Example 6 propylene 15 37 18 41 glycol n- butyl ether (DOWANOL PnB) Example 7 propylene 12 36 11 37 glycol n- propyl ether (DOWANOL PnP) *The Reference Final Wt % Recovery was slightly higher in this set of experiments presumably because the temperature of the steam injected into the oil sand was higher as a result of injecting only steam without a stream of liquid water. ** NM means not measured.

Examples 8-21

(32) For the Reference, pack 50 grams of oil sand (as described in previous examples) into a metal mesh basket and suspend the basket within a Parr reactor containing 150 milliliters of water so that the basket is above and does not contact the water. Heat the Parr reactor using a heating mantel regulated with a temperature controller. Using the temperature controller heat the contents of the Parr reactor to 188° C. over a period of half of an hour and maintain at that temperature for an additional four hours. Turn the power to the heating mantel off and let the Parr reactor and contents cool overnight (approximately 7 hours) to room temperature (approximately 22° C.). Measure the amount of bitumen extracted from the oil sand by toluene extraction of the liquid within the Parr reactor. Approximately 15 wt % of the bitumen in the oil sands is extracted.

(33) For Examples 8-21, repeat the procedure for the Reference except include either 3.75 grams or 15 grams of alkylene glycol ether additive (see Table 3) in the water within the Parr reactor to provide a mixture that is approximately 2.5 wt % or 10 wt % alkylene glycol ether, respectively.

(34) The wt % oil recovery from the oil sands sample using this procedure is reported in Table 3. While the absolute recovery percentages may change in actual in situ subterranean steam extraction, the trends represented in Table 3 are expected to be representative of in situ processes. That is, additives showing higher recovery percentages in this experiment than the reference are expected to show higher recovery percentages in an in situ subterranean steam extraction relative to a recovery process without the additive.

(35) TABLE-US-00003 TABLE 3 Wt % Wt % Recovery for Recovery for 2.5 wt % 10 wt % Alkylene Glycol alkylene alkylene Sample Ether Additive glycol ether glycol ether Reference (none) 15 15 Example 8 propylene glycol 34 Not Measured n-propyl ether (NM) (DOWANOL PnP) Example 9 propylene glycol 30 NM n-butyl ether (DOWANOL PnB) Example 10 propylene glycol 44 90 n-hexyl ether Example 11 propylene glycol 71 99 phenyl ether (DOWANOL PPh) Example 12 propylene glycol NM 50 phenyl ether (DOWANOL PPh) Example 13 dipropylene glycol 25 NM n-propyl ether (DOWANOL DPnP) Example 14 dipropylene glycol 44 NM n-butyl ether (DOWANOL DPnB) Example 15 dipropylene glycol 52 96 n-hexyl ether Example 16 dipropylene glycol 59 89 2-ethylhexyl ether Example 17 tripropylene glycol 30 NM n-propyl ether Example 18 tripropylene glycol 54 NM n-butyl ether Example 19 Butylene glycol NM 36 methyl ether Example 20 Butylene glycol 40 98 n-propyl ether Example 21 Butylene glycol 28 100  n-butyl ether