CA1085601A - Enhanced oil recovery using alkaline sodium silicate solutions - Google Patents

Abstract

"Abstract of the Disclosure"
An enhanced oil recovery process for subterranean reservoirs wherein there is injected into the reservoir a relatively large slug of a dilute aqueous alkali metal sili-cate solution. It is optional to follow the said silicate solution with an aqueous drive fluid. In treating hetero-geneous reservoirs, it is further optional to also inject a small slug of a dilute aqueous solution of an agent that re-acts with the alkali metal silicate to form a gelatinous precipitate. In the latter instance a small spacer slug of water is injected between successive slugs of the reactant solutions to separate the reactants during injection.

Description

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This inv~n-tion relates to the recovery of petroleum from subterranean reservoirs, and more particularly to an enhanced oil recovery process especially suitable for hetero-geneous reservoirs.
It has long been recognized that substantial amounts of oil remain unrecovered at the completion of normal primary recovery operations. In order to improve the recovery o~ oil, it is common practice to supplement the native reservoir energy by various enhanced recovery means including the use of various aqueous fluids to displace oil from a formation.
It is known to use small slugs of a dilute aqueous alkaline alkali metal silicate solution in various enhanced ;
oil recovery processes. U. S. Patents 3,805,893 issued April 23, 1974 and 3,871,452 and 3,871,453 issued March 18, 1975 involve, in part, injection into a subterranean petroleum `
reservoir of small slugs of a dilute aqueous solution containing from about 0.01 to 0.8 weight percent of an alkaline alkali metal silicate having a molar ratio of M20/SiO2 of 1 or above, wherein M is an alkali metal atom. It is suggested that the solution be injected for from 1 hour to 7 days at a rate of from 100 to 2,000 barrels per day per well. U. S. Patent 3,920,074 issued November 18, 1975 suggests the use of 0.005 to 0,8 weight ;
; percent of the same silicate material. It is further suggested that the composition be injected at the rate of about 0.1 to 10 barrels/foot of vertical formation thickness. These patents teach the use of the composition to reduce oil saturation in the formation and, in conjunction with an agent such as calcium - chloride which reacts with the silicate material, to form plug-; ging precipitates as part of an oil recovery process. In the various patents, the aqueous solution of the silicate may be injected alone or as an ingredient of an emulsion. In some patents the aqueous silicate solution is followed by a water drive. In all instances the aqueous silicate solution is used ~n slugs having a relatively small volume.

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While these processes have utility in recovering additional quantities of oil from su~terranean petroleum reser~
voirs, nevertheless, it is desirable to even further increase the amount of oil recoverable from these reservoirs. ~ ;
Accordingly, a principal object of this invention is to provide an improved process or enhanced oil recovery from a subterranean reservoir. ;' Another object of the invention is to provide an improved process ~or enhanced oil recovery from a heterogeneous - 10 subterranean formation.
A further object o~ the invention is to provide such a process wherein channeling of the injected enhanced recovery ; fluid is reduced.
` A still further object of the invention is to provide ... .
such a process which is especially suitable for recovering oil having a relatively high acid number.
Other objects, advantages and features will be ~-~ - .
apparent from the following description.

Briefly this invention involves a process for the ,....................................................................... . .
enhanced recovery of oil from a heterogeneous subterranean reservoir penetrated by at least one injection well and at least one production well spaced therefrom which comprises:
(a) alternately injecting through the injection well and into the reservoir small slugs of:
(1) a dilute aqueous solution of an alkaline alkali metal silicate having a molar ration of M2O/SiO2 of 1 or above wherein M is an alkali metal -atom which aqueous solution of alkaline alkali metal silicate reduces the interfacial tension of said oil with water at high pH to about 0.1 dyne/cm or less,

(2) water;

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(3) a dilute aqueous solution of a water-soluble material that reac$s with the alkali metal silicate to form a precipitate;

(4) water: and (b) injecting about 0.1 to about 1 reservoir pore volume of a dilute a~ueous solution of said alkaline alkali metal silicate.
Fuxther, this invention contemplates a process for : the enhanced recovery of oil from a subterranean reservoir ;:
. 10 wherein there is injected into the reservoir through one or : more injection wells a relatively large slug of a dilute .
~ aqueous alkali metal silicate solution comprising about 0.1 ``~ to about 1 reservoir pore volume, preferably about 0.15 to -.~ about 0.4 reservoir pore volume, and oil is recovered from .-spaced production wells. The said silicate solution can make up the entire drive fluid or can be followed by a drive fluid. .
: A preferred procedure for heterogeneous reservoirs includes -,: ,, -:
injection of a relatively small amount of the said silicate solution, followed by a relatively small slug of a dilute .
aqueous solution of an agent that reacts with the said silicate . to form a gelatinous precipitate, followed by a relatively large slug of the said silicate solution. A small slug of : ' ':
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-2a-~1~)8~i6(11 water is injected between su~essive slugs of the reactant solutions as a spacer to separate the reactants during injection.
FIG. 1 is a graph illustrating the variation in the pH of aqueous solutions of various alkaline sodium silicates and sodium hydroxide as a function of the concentration of the alkaline material; and FIG. 2 is a graph illustrating the variation in -the interfacial tension of a particular crude oil as a function of pH~
~`~ 10 According to -the present invention, an improved ~- enhanced oil recovery process for subterranean reservoirs is accomplished by displacing the oil in the reservoir with a relatively large slug of a dilute aqueous alkali metal silicate s~lution. This silicate solution may be the only displacement fluid employed or it may be followed by a drive fluid. In heterogeneous formations, it is preferred to interrupt the -;
injection of the large slug of silicate solution after only a small volume thereof has been injected, inject a small slug of a dilute aqueous solution of an agent that reacts with the silicate to form a gelatinous precipitate, which solution is both preceded and followed by a small spacer slug of water, and then resume the injection of the silicate solution.
Crude petroleum is known to contain varying amounts -~
of organic acid materials which react wi-th alkaline materials -to form soaps that reduce the interfacial tension between the crude petroleum and water. This reduction in interfacial tension enables solutions containing alkaline materials to more ;~
easily displace residual oil from the pores of a reservoir.
The petroleum acids found in any particular crude petroleum can include various carboxylic acids and phenolic acids. Saponi-fication of these acids form surface active agents that reduce the interfacial tension between the crude petroleum and water.

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The amount of these saponifiable materials in a crude petroleum and their effect upon the surface active properties of the system can be ~haracteriæed by the acid number of the crude petroleum. The acid number is defined as the number of milli-grams of potassium hydroxide required to neutralize the acid in one gram of sample. The method of this invention is par-tic-ularly applicable to the recovery of crude petroleum that has a sufficient quantity of naturally occurring organic acids to exhibit an interfacial tension with water at a high pH of 0.1 .
dyne/cm or less. A crude oil having an acid number of greater than about 0.1, preferably about 0.2 to about 10, generally gives these low interfacial tensions.
Also, it is well known that high viscosity crude ~, . ;,~, petroleum is less amenable to recovery by waterflooding than `
~-, the lower viscosity oils. While the method of this invention f` j1 can be efficaciously employed to recover low viscosity crude -~
petroleum, it has particular application in the recovery of crude petroleum exhibiting a viscosity above that of the flood water under reservoir conditions of temperature and pressure, ;
and more particularly above about 5 centipoises at reservoir -conditions. ~
The method of th s invention can be adapted for -recovery of oil from heterogeneous reservoirs~ As most petroleum reservoirs exhibit some heterogeneity, the overall ~ ;
recovery efficiency of the displacement process is improved ;
in most naturally occurring petroleum reservoirs by treatment with the process of this invention. By heterogeneity, it is meant that the reservoir is comprised of stratified layers of varying permeability, or that it contains fractures, cracks, , fissures, streaks, vuggs, or zones of varying permeability that cause an injected flooding medium to advance through the reser-voir nonuniformly. Thus, the formations that are particularly amenable to treatment by the me~hod of this invention are those -4- -~

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formations that have strata or zones of different permeabilities, and particularly ~ormations having strata varying more than about 50 millidarcies in permeability or which are otherwise structurally ~aulted to the extent that the injected flooding media does not advance through the formation at a substantially -uniform rate along the entire flood front, but which instead are susceptible to channelling of the flood water to the producing `` well.
The alkaline alkali metal silicate employed in the practice of this invention for injec-tion in-to the reservoir is an alkali ~etal silicate having a molar ratio of M2O/SiO2 of 1 and above, particularly from about 1 to about 4 and most prefer-ably from about 1.5 to about 2.5, wherein M is an alkali metal atom, such as sodium, potassium, lithium, cesium and rubidium, exemplary of which are alkali metal orthosilicate, alkali metal metasilicate, alkali metasilicate pentahydrate, and alkali metal sequisilicate. Particular agents useful in the practice of the invention include sodium and potassium orthosilicate, sodium and potassium metasilicate, sodium and potassium metasilicate ;
pentahydrate, and sodium and potassium sequisilicate. The pH
of aqueous solutions containing various concentrations of alkaline sodium silicates are shown in FIG. 1. These alkaline sodium silicates generally provide lower pH solutions than equal weight concentration solutions of sodium hydroxide, but nevertheless, provide high pH solutions useful in reducing the interfacial -~
tension of many crude petroleum-water systems. The reductions in interfacial tension between the silicate solution and a Texas crude 3il are shown in FIG. 2. Sodium orthosilicate is a particularly preferred alkaline alkali metal silicate because of its relatively high pH and correspondingly low interfacial tension with crude oils containing natural organic acids.

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With most crude oils containing a significant quantity of saponifiable materials, i.e., those having an ac~d number of about 0.1 to about lO, significant oil recovery can be achieved by use of an aqueous solution containing about 0.1 to about 2 weight percent of alkaline alkali metal silicate. Preferably an ;
aqueous solution containing about 0.5 to 1.5 weight percent '~
alkaline alkali metal silicate is employed.
`` The alkaline alkali metal silicates used in the practice of this invention are available in solid form, and the respective alkaline alkali metal silicate solutions can be prepared by dis-solving an appropriate quantity of the alkaline alkali metal silicate in water. However, in many cases it is more convenient - and less costly to prepare the alkaline alkali metal silicate by . adding caustic to an aqueous solution of a low-alkalinity alkali -~
metal silicate having a M2O/SiO2 ratio of less than 1.
Where the alkali metal silicate aqueous solution is -~
followed by drive fluid, conventional flooding agents may be used in a conventional manner. Accordingly, the flooding medium can be water, brine, or a dilute aqueous solution of a water-soluble -~ 20 polymer exhibiting a viscosity greater than that of the water or brine; the flooding medium being injected through one or more injection wells to displace oil towards one or more spaced ~
production wells. A number of water-soluble polymers are known ;
to decrease the mobility of water in porous media when dissolved ;
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therein in relatively dilute concentrations. Water-soluble ~ -polymeric materials that can be employed are relatively high molecular weight acrylic acid-acrylamide copolymers, acrylic `
acid-acrylamide-diacetone acrylamide terpolymers, partially hydrolyzed polyacrylamides, hydroxyethyl cellulose, carboxymethyl 30 cellulose, polyacrylamides, polyoxyethylenes, modified starches, heteropolysaccharide obtained by the fermen-tation of starch derived sugar, polyvinyl alcohol, polyvinyl pyrollidone, and polystyrene sulfonates.

iL~8~6(~1 In treating the more heterogenous reservoirs, it is preferred to plug or greatly reduce the flow in the more permeable portions of the reservoir during the treatment so that subsequently injected silicate solution enters the less permeable portions of the reservoir to displace oil wh.ich mi.ght otherwise be bypassed by the enhanced recovery fluids. ~ wide variety of reagents can be employed -to react wi-th the alkaline alkali metal silicate to form the plug or mobil.i-ty adjus-ting precipitate, inclusive of which are acids and acid precursors such as chlorine, sulfur dioxide, sulfur -trioxide; water-soluble salts of bivalent metals such as the halide and nitrate salts of iron, aluminum, calcium, cobalt, nickel, copper, mercury silver, lead, chromium, zinc, cadmium and magnesium; and water-soluble ammonium salts. A preferred agent for reactlon with the alkaline alkali metal silicate is calcium chloride.
Preferably, approximately the same volumetric quantities of each aqueous reactant solution are injected in each injection `
cycle, with the concentration of the water-soluble agent that reacts with the alkaline metal silicate being adjusted to provide sufficient agent to stoichoimetrically react with the sillcate.
In carrying out the plugging treatment, each slug of reactant solution is injected at conventional flood water in-jection rates such as rates of about 100 to 2,000 barrels per day for a period of about 1 hour to about 7 days, and preferably for a period of about 4 hours to 1 day. The water slug injected intermediate the slugs of reactive solutions can be injected in smaller volume. The following is a typical injection cycle:

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~ Time - ; ;
Slu~ Broad Range Preferred Range -~ :
Alkaline alkali metal 1 hour to 7 days 4 hours to 1 day silicate solution i ;
Water 1 hour to 1 day 1 to 8 hours Aqueous solution of .
reactant 1 hour to 7 days 4 hours to 1 day water 1 hour to 1 day 1 to 8 hours It has been found in some instances that the injection pressure increases during the alkaline alkali metal sllicate solution injection step, and then decreases to its original value -~
during the remaining injection steps of that cycle, rising again ,, ,: .
upon the next injection of alkaline alkali metal silicate solu~
tion. Thus, in some instances the slug injection times must be sufficiently short to prevent excessive injection pressures.
In a preferred mode of practicing the inven-tion to recover oil from a subterranean reservoir, an aqueous solution ;
of sodium orthosilicate is prepared having a sodium orthosilioate concentration selected to provide a pH sufficient to reduce the `
interfacial tension of a selected oil-water system to less than 0.1 dyne/cm, and preferably to a value of less than 0.01 dyne/cm. -The sodium orthosilicate solution is injected into the reservoir through an injection well for a period of time until about 0.15 to about 0.4 pore volume o~ solu-tion has been injected. Flood water or brine is then i~jected to drive the silicate solution through the reservoir. In another mode of practicing the inven-tion, injection of the relatively large slug of silicate solution is preceded by the typical injection cycle shown above wherein a plug or mobility adjusting precipitate is formed. This typical injection cycle could be repeated later in the flooding operation `
if severe fluid channeling of injected fluid to the producing well ! ' occurs. The oil and other produced fluids are recovered from a ;~
spaced production well. While the alkaline silicate solution treatment is normally followed by conventional water drivQ, it 8~6(3~ ~

has been found in some instances that the subsequently injected flood water soon breaks through to the producing wells. Hence, it may be necessary to maintain the alkaline silicate solution injection for substantially -the entire recovery operation.
This invention is further illus-trated by the following examples which are illustrative of specific modes of practicing -the invention and are not intended as limiting the scope of the invention as defined by the appended claims.

A 2 inch square by 4 foot long Dundee sandstone test ~
core is first saturated with a synthetic brine containing 7.5 ;
weight percent sodium chloride, 1.5 weight percent calcium chloride and 0.~ weight percent magnesium chloride, and then `
with a Texas crude oil having an acid number of 1.1. The inter-facial tension of this crude oil as a function of pH is shown in FIG. 2. The core is then flooded wi-th the same synthetic brine to residual oil satura-tion. Various flooding operations are then carried out wherein, as part of the operations, various amounts of an aqueous solution containing 0.5 weight percent of Metzo 200t, a sodium orthosil~cate, marketed by the Philadelphia Quartz Company are injected. The flooding operation is completed by injecting fresh water to residual oil saturation. The produced fluids are recovered and the oil recovery determined. In Example 1, a relatively small slug, 0.1 pore volume, of the sodium ortho-silicate solution is used as taught by the prior art. In Example 2, there is used a relatively large total volume of injected fluids, 0.5 pore volume, made up of alternate slugs of 0.01 pore volume sodium orthosilicate solution followed by 0.01 pore volume of an aqueous solution containing 0.035 weight percent of calcium chloride. This procedure is also taught by the prior art. In Example 3, a relatively large slug, 0.5 pore volume, of the sodium orthosilicate solution is injected as taught by this in- `
vention. The results of these tests are summarized in Table 1.
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Example Number Slug size, pore volume 0.1* 0.5** 0.5**~
~ Oil recovery, ~ residual oil O 0 16 ; * Aqueous solution containing 1.0 weight percent of sodium -~
orthosilicate.
. , ** Alternate slugs of 0.01 pore volume of an aqueous solution containing 0.5 weight percent of sodium orthosilicate and `
0.01 pore volume of an aqueous solution containing 0.035 -~ weight percent of calcium chloride. ;
*** Aqueous solution containing 0.5 weigh-t percent of sodium -~ orthosilicate.
These results illustrate the effectiveness of the method of this invention as compared to the methods of the prior art.
EXAMPLES 4 to 7 .
A 1.5 inch square by 4 foot long Berea sandstone tes-t ;~
core is satura-ted with synthetic brine, then with crude oil and then 100ded with synthetic brine to residual oil saturation as described above using crude oils having various acid numbers.
; A slug of aqueous Metzo 200t sodium orthosilicate, solution is injected into the tPst core followed by fresh water to residual `~
oil saturation. The produced fluids are recovered and the oil recovery determined.

ExamPle Number Crude oil usedTexas Oklahoma Kansas Kansas Acid number of crude oil 1.1 0.11 0.05 0.05 Concentra-tion Metzo 200~ 0.5 0.3 0.3 0.8 -in aqueous solution (weight %) ~
Slug size, pore volume 0.4 3.0 10 10 - -Oil recovery, 18 2 0 0 % residual oil t Trademark :

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It is apparent from these examples that oil recovery is greatly affec-ted by the acid number of the crude oil.
Various embodiments and modifications of this invention have been described in the foregoing description and examples, and further modifications will be apparent in those skilled in the art. Such modifications are included within the scope ~
of this invention as defined by the following claims. `~ ~.
Having now described the invention. I claim:

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Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the enhanced recovery of oil from a heterogeneous subterranean reservoir penetrated by at least one injection well and at least one production well spaced therefrom which comprises:
(a) alternately injecting through the injection well and into the reservoir small slugs of:
(1) a dilute aqueous solution of an alkaline alkali metal silicate having a molar ratio of M2O/SiO2 of 1 or above wherein M is an alkali metal atom which aqueous solution of alkaline alkali metal silicate reduces the interfacial tension of said oil with water at high pH to about 0.1 dyne/cm or less;
(2) water;
(3) a dilute aqueous solution of a water-soluble material that reacts with the alkali metal silicate to form a precipitate;
(4) water; and (b) injecting about 0.1 to about 1 reservoir pore volume of a dilute aqueous solution of said alkaline alkali metal silicate.

2. The process defined in claim 1 wherein said oil has an acid number of greater than about 0.1.

3. The process defined in claim 1 wherein said small slug of dilute aqueous solution of alkaline alkali metal silicate and said dilute aqueous reactant solution are injected at a normal water injection rate for a period of about 1 hour to about 7 days, and said water slugs are injected for a period of about 1 hour to about 1 day.

4. The process defined in claim 1 wherein the dilute aqueous solution of alkaline alkali metal silicate injected both in step (a)(1) and step (b) contains about 0.1 to 2 weight percent alkaline alkali metal silicate.

5. The process defined in claim 1 wherein the alkaline alkali metal silicate is sodium orthosilicate.

6. The process defined in claim 1 wherein the injection of the dilute aqueous solution of alkali metal silicate injec-ted in step (b) is followed by a slug of aqueous drive fluid.

7. The process defined in claim 6 wherein the aqueous drive fluid is water.