Phosphites and phosphates of 3-sulfoxy-1,2-propylene glycols

Phosphites and phosphates of 3-sulfoxy-1,2-propylene glycols are taught as new compositions of matter. These compounds are useful as co-surfactants in enhanced oil recovery.

FIELD OF THE INVENTION 
This invention relates to phosphites and phosphates of 
3-sulfoxy-1,2-propylene glycols. More particularly, this invention relates 
to phosphites and phosphates of 3-sulfoxy-1,2-propylene glycols wherein 
the said phosphites and phosphates are of the formulas 
##STR1## 
wherein R is selected from the group consisting of an alkyl moiety of 1 to 
24 carbon atoms and aryl moieties of 6 to 24 carbon atoms, the ring 
radicals of said aryl moieties being selected from the group consisting of 
phenyl, biphenyl, naphthalene, anthracene and phenanthrene radicals, 
wherein n is 1, 2, or 3; m is 0, 1, or 2; and the sum of n+m is 3. 
Preferably R is selected from the group consisting of a phenyl moiety, an 
alkyl moiety of from 8 to 12 carbon atoms and which is preferably n-octyl 
to n-dodecyl. 
For convenience these compounds are referred to as phosphites and 
phosphates of 3-sulfoxyl-1,2-propylene glycols. These compounds possess 
biocidal properties. The invented compounds of molecular weights within 
the range of from about 400 to about 1000 act as cosurfactants useful in 
enhanced oil field recovery. These compounds are also useful as 
surfactants and biocides, and can be used as hydraulic fluids when of 
sufficiently low molecular weight, and as chemical intermediates. 
Cosurfactants function as coupling agents for surfactants and reservoir 
brines for the purpose of enhancing crude oil production. Surfactant and 
cosurfactant mixtures are dissolved in brines in low concentrations to 
form micellar fluids or solutions. These micellar solutions can be 
described as microemulsions containing surfactants which act to reduce the 
interfacial tension between water and oil. A second component, a 
cosurfactant, usually an alcohol, is used to improve the quality of the 
micellar solution. An efficient cosurfactant increases the micelles' 
capacity to solubilize more oil or water and still form stabilized 
solutions. 
Compounds used as cosurfactants in the prior art have been alcohols such as 
isopropyl alcohol, amyl and hexyl alcohols and their ethoxylated 
derivatives. These cosurfactants have limited capabilities because of the 
variety of reservoir conditions encountered in enhanced oil recovery 
programs. For example, special systems must be designed for reservoirs 
which are essentially fresh water, that is, those which contain 6000 ppm 
or less monovalent ions, and those which are essentially hard water, those 
which contain 50,000 ppm monovalent ions plus 500 ppm or more divalent 
ions. Cosurfactants should perform so as to achieve a stable fluid when 
the water-cosurfactant mixture is in contact or mixed with crude oil. 
Molecular weight of the cosurfactant should be sufficiently low to permit 
passage through semipermeable rock formations and achieve mobility 
control. 
This invention accordingly also relates to a new and unique family of low 
molecular weight compounds which are suitable for use as cosurfactants for 
enhanced crude oil recovery. These compounds in use lower the interfacial 
tension between water and oil, are low molecular weight, of from about 400 
to about 1200, and are required in only low concentrations to formulate 
micellar fluids. 
BACKGROUND OF THE INVENTION 
Beta-hydroxyalkylsulfoxides to which class the 3-sulfoxy-1,2-propylene 
glycol phosphites and phosphates of my invention belong, can be prepared 
by the the method of Anderson, U.S. Pat. No. 3,247,258, which is 
incorporated by reference, wherein the mercaptan (or thiol), the olefinic 
compound and oxygen are in contact at temperatures above 80.degree. C. 
Anderson indicates that with certain olefins and mercaptans such as 
indene, styrene and thiophenol, the reaction occurs by mixing the olefin 
and mercaptan first, with the oxygen being bubbled through the mixture 
thereafter. Other patents such as Oswald, et al., U.S. Pat. No. 3,043,824 
and Goodhue, et al., U.S. Pat. No. 3,210,243, which are each incorporated 
by reference, disclose preparing beta-hydroxyalkylsulfoxides through (1) a 
co-oxidation route using a hydroperoxide or through (2) oxidation of the 
sulfide by means of hydrogen peroxide. Oswald indicates that the 
preparation of hydroperoxide products by olefin-mercaptan co-oxidation to 
the sulfoxide requires chain initiators, e.g., ultraviolet light and the 
addition of peroxide compounds (hydroperoxides). In the absence of such 
catalysts, some co-oxidation reactions have extremely long induction 
periods and are not practical to carry out. Goodhue teaches that 
preparation of the sulfoxide using hydrogen peroxide is a three-step 
synthesis through the sulfide which in turn is prepared from the mercaptan 
with epichlorohydrin. Fields, in commonly-assigned U.S. Pat. No. 
4,040,921, incorporated herein by reference, teaches a one-step process 
for beta-hydroxyalkylsulfoxides by reacting an olefin and a thiol with 
oxygen in the presence of a dye sensitizer using visible light at a 
temperature from -10.degree. C. to 70.degree. C. 
The object of this invention accordingly is to produce as new compounds the 
phosphites and phosphates of 3-sulfoxy-1,2-propylene glycols. These 
compounds are useful as cosurfactants in enhanced oil recovery, as 
surfactants and biocides, and as hydraulic fluids when of sufficiently low 
molecular weight. 
SUMMARY OF THE INVENTION 
This invention relates to phosphites and phosphates of 
3-sulfoxy-1,2-propylene glycols which are useful as cosurfactants in 
enhanced oil recovery, surfactants and biocides, and as hydraulic fluids 
when of sufficiently low molecular weight. 
DETAILS OF THE INVENTION 
The phosphites and phosphates of 3-sulfoxy-1,2-propylene glycols can be 
prepared by reacting thiols, olefinic phosphites or olefinic phosphates 
and oxygen according to the method of Fields, U.S. Pat. No. 4,040,921 or 
by the methods of Anderson, U.S. Pat. No. 3,247,258 or Goodhue, et al., 
U.S. Pat. No. 3,210,243. 
The phosphite and phosphate 3-sulfoxy-1,2-propylene glycols can be 
aliphatic, aromatic, or heterocyclic beta-hydroxysulfoxides containing 
substituents such as halo, nitro, cyano, or carboalkoxy groups. They are 
prepared readily by reacting olefinic phosphites or olefinic phosphates, 
thiols, and oxygen in the presence of a dye sensitizer and light, 
according to the equation for the reaction of 1 mole of phosphite with 3 
moles of thiol and oxygen: 
##STR2## 
The thiol (or mercaptan) an be aliphatic, aromatic, alicyclic and 
heterocyclic and can be described as being of the general formula RSH. R 
can be a moiety of from 1 to 40 carbon atoms. R preferably is a moiety of 
from 1 to 24 carbon atoms, from methyl to tetracosyl moieties. Examples 
of such thiols are methylthiol, ethylthiol, n- and isopropylthiol, n-, 
sec- and tert-butylthiol, n-hexylthiol, n-octylthiol, tert-octylthiol, 
n-dodecylthiol, n- and tert-hexadecylthiol, cyclohexylthiol, 
tetracosylthiol, thiophenol, thiocresol, 4-n-dodecylthiocresol, 
4-tert-nonylthiocresol, pyridine-2-thiol, pyridine-4-thiol, 
thiophene-3-thiol, furan-2-thiol, quinoline-2-thiol, quinoline-4-thiol, 
phenanthridine-1-thiol, 1,3,5,triazine-2-thiol. 
Preferably the thiol comprises a thiol containing 1 to 18 carbon atoms. 
These are preferred because they are cheap, reactive and extend the range 
of derivatives to cover these solubles in various inorganic and organic 
solvents. One or more hydrogens of the aliphatic, alicyclic and aromatic 
moieties such as methyl, ethyl, isobutyl, tolyl and phenyl moieties of the 
above-described thiol compounds can be replaced with non-reactive radical 
groups such as halogens and nitro radicals and, on the alicyclic and 
aromatic moieties, by alkyl moieties. 
The molar ratios of the reactants to prepare the 3-sulfoxy-1,2-propylene 
glycols, i.e., the thiols, olefins, oxygen that can be used, can vary 
considerably. The thiol-olefin ratio is between 0.001 to 5 moles of thiol 
per mole of olefin. Substantially equimolar amounts of olefin and thiol 
are preferred. Use of a solvent such as heptane, hexane, benzene, acetone, 
or dioxane at concentrations of 1 to 85 weight percent is convenient. When 
water-miscible solvents such as acetone or dioxane are used, water up to 
50% by weight of organic solvent may be incorporated. In such cases, or 
when water is used with immiscible solvents such as heptane or benzene up 
to 50% by weight, phase-transfer agents such as cetyl trimethyl ammonium 
bromide, benzyl triethyl ammonium chloride, benzyl triphenyl phosphonium 
chloride, etc., are incorporated at concentrations of 0.001 to 1% by 
weight of total solvent. 
Heptane is the preferred solvent: 10 to 40 weight percent is the preferred 
concentration range of the reactants. 
It is essential that at least one optically sensitizing dye be used in 
conjunction with the application of visible light. The term dye sensitizer 
can be defined as being an organic dye which increases spectral response. 
Typical dye sensitizers are fluorescein derivatives, methylene blue, 
certain porphyrins and polycyclic aromatic hydrocarbons. Suitable dye 
sensitizers include Rose Bengal, methylene blue and Eosin. 
Rose Bengal and methylene blue are the preferred dye sensitizers dissolved 
in acetone at 0.1-5% by weight. Sufficient dye is added to give final 
concentrations of 0.02 to 1% by weight in the total reaction mixture; 0.05 
to 0.25% by weight is preferred. Alternatively the dye may be introduced 
bound to an ion-exchange resin in a relatively insoluble form, e.g., 
anionic Rose Bengal or Eosin attached to the strongly basic anion exchange 
resin Amberlite IRA-400 (Rohm and Haas, Philadelphia) or cationic 
methylene blue attached to the strongly acidic cation exchange resin 
Amberlite IRC-200 (J. R. Williams et al., Tetrahedron Letters, 4603 
(1973)). 
The reaction may be run in any type of open or sealed vessel, suitably 
agitated. A particularly useful apparatus for the reaction is the Parr 
Pressure Reaction Apparatus, Item No. 3911, made by the Parr Instrument 
Company of Moline, Ill. This apparatus consists of a heavy-walled clear 
Pyrex bottle connected with a tank of oxygen under pressure; the bottle is 
shaken vigorously during the reaction. Pressures of oxygen of 1 to 250 
psig may be used; 15 to 50 psig O.sub.2 are convenient pressures in the 
laboratory although, commercially, pressures over 100 psig are preferred. 
The bottle is illuminated with visible light such as ordinary incandescent 
or photoflood bulbs of 50-500 watts, preferably mounted in reflector with 
the light source 11/2 to 3 inches from the vessel. 
The lamps used were General Electric 500 watt photoflood or incandescent 
bulbs and a General Electric 275 watt sunlamp. Specifications of the G.E. 
500 watt photoflood lamp require 1.61 radiated watts from 280 to 400 
nanometers, and 6.9 radiated watts from 400 to 700 nanometers, the range 
of visible light. The G.E. sunlamp has 4.47 radiated watts in the 
ultraviolet range from 280 to 400 nanometers, and 7.03 radiated watts in 
the visible light range of 400 to 700 nanometers. 
Reaction is continued until the calculated amount of oxygen has been 
absorbed as shown by pressure drop; times of 1 to 100 hours may be used, 
depending on the nature of the thiol and the pressure of oxygen. Workup 
generally consist of evaporating the reaction mixture at 
30.degree.-60.degree. C. and 0.1-1 Torr, conveniently in a rotating RINCO 
evaporator (BUCHI Vacuum Rotary Evaporator ROTAVAPOR EL, Rinco Instrument 
Company, Inc., Greenville, Ill.). 
The present invention also comprises a method of injecting a micellar slug 
into a subterranean formation comprising the steps of (1) contacting said 
subterranean formation with an aqueous fluid composition comprising water, 
a surfactant, a hydrocarbon, an electrolyte and a low molecular weight 
compound within the range of from about 400 to about 1000 of a 
beta-hydroxyethylsulfoxide; (2) applying sufficient pressure to said 
composition to cause said micellar slug to move through said formation; 
(3) maintaining sufficient pressure while injecting said composition into 
said formation. The said low molecular weight compounds can be selected 
from the group consisting of phosphites and phosphates of 
3-sulfoxy-1,2-propylene glycols. 
In order to facilitate a clear understanding of the invention, the process 
of preparing phosphites and phosphates of 3-sulfoxy-1,2-propylene glycols 
and the use thereof, the following specific embodiments are described in 
detail. It should be understood, however, that the detailed expositions of 
the instant invention, while indicating preferred embodiments, are given 
by way of illustration only since various changes and modifications within 
the spirit and scope of the invention will become apparent to those 
skilled in the art from this detailed description. 
PRELIMINARY EXAMPLE 
Screening tests for suitable cosurfactants to be used as additives for 
enhanced oil recovery have been developed which indicate a relationship 
exists between interfacial tension of the cosurfactant and petroleum 
removal from core samples using a micellar solution. Surfactant-stabilized 
dispersions of water in hydrocarbon are micellar solutions. In addition to 
the required surfactant, water and hydrocarbon micellar solutions can 
contain cosurfactants and electrolytes to improve stability. Alcohols such 
as isopropanol and amyl alcohols typically have served as cosurfactants. 
Sodium chloride and sodium sulfate are examples of electrolytes that are 
used. 
Important aspects of a micellar solution include an ability to solubilize 
water, compatibility with hydrocarbon and crude oil, an increasing 
viscosity with increased water concentration and inversion to an 
oil-in-water solution. In a micelle, surfactant and cosurfactant surround 
dispersed water which exists in the hydrocarbon phase as spherical 
droplets. With additional water, the water droplets increase in size. When 
water is the dispersed phase, the micellar solutions exhibit 
hydrocarbon-like properties of the external phase. As more and more water 
is solubilized in a micellar system, spheres enlarge until inversion takes 
place to form an oil-in-water emulsion. Cosurfactants in a micellar 
solution stabilize the solution to reduce incidence of inversion and phase 
separation. 
The following bench test has been devised as a preliminary vial screening 
test to eliminate need for expensive core tests of cosurfactants. The test 
has been found to have reliability in predicting suitable properties of 
cosurfactants when used in micellar solutions. The principal important 
aspect has been found to be the interfacial tension of the cosurfactant in 
an oil-water mixture. The formulation is required to yield stable fluids 
in brine and to show low interfacial tension (IFT) as well as very good 
miscibility with crude petroleum. 
Micellar fluids formulated from concentrates containing 40:1 to 5:1 
surfactant-cosurfactant ratios have been tested over a wide range of 
salinities (sodium chloride in water) and hard waters, being examined for 
phase stability, fluid clarity, interphase behavior and miscibility of 
aqueous fluids with crude petroleum. 
The vial screening bench test is an empirical test which comprises mixing 
the micellar fluid and crude petroleum by swirling the fluids together in 
a test tube while observing the interface. A light source is used to 
observe the fluid-oil behavior. The interfacial mixing (and hence 
interfacial tension) is judged upon a scale of very low, moderately low, 
low, medium and high by a comparison with standards previously developed. 
For example, brine solutions of a hardness range from under 6,000 ppm of 
monovalent ions (sodium chloride) to about 50,000 ppm of monovalent ions 
(sodium chloride) plus 500 ppm of divalent ions (calcium chloride) are 
mixed with a 40:1 ratio of surfactant-cosurfactant mixture with Second 
Wall Creek crude. The surfactant is a petroleum sulfonate. 
Surfactant-cosurfactant-brine mixtures are prepared at ambient temperature 
and pressure. 
Stability of the brine solution with surfactant-cosurfactant mixture is 
tested by pouring the mixture into a 50 ml graduated cylinder and allowing 
the solution to stand for one hour undisturbed. Fluids which remained 
single phase and free of sediment are further tested. 20 ml of solution 
are poured into a vial. 4 ml of crude petroleum are added to the vial. The 
vial is turned gently, observing mixing behavior of crude and micellar 
fluid. The vial is then shaken vigorously for one minute, after which the 
vial is allowed to stand undisturbed for one hour. After this period, the 
fluid is evaluated for oil drop-out, number of liquid phases, thickness of 
emulsion and miscibility. Results are correlated with interfacial tension 
of solution and crude by visual observation and spinning drop method of J. 
L. Caylas, et al., "Low Interfacial Tension," American Chemical Society 
Series No. 8 Adsorption At Interfaces, 1975. Formation of round oil 
droplets which separate quickly, and failure to form an emulsion, indicate 
a high, ineffective interfacial tension characteristic which can render 
the cosurfactant unsuitable as an additive for enhanced oil recovery 
applications.

EXAMPLE I 
A mixture of 20.2 g (0.1 mole) of triallyl phosphite, 6.94 ml. of 
thiophenol, 100 ml of n-heptane, and 10 ml of 0.25 wt% of Rose Bengal in 
acetone was shaken under 25 psig O.sub.2 at 25.degree. C. while being 
irradiated by a G. E. Sunlamp for 16 hours, during which time 5 lbs. 
O.sub.2 were absorbed. The mixture was filtered, the evaporated to 
constant weight in a Rinco evaporator at 50.degree. C. and 0.2 torr. The 
product was a light brown, moderately viscous oil, 33.8 g., 98 mole % 
yield. 
Analysis. Calcd. for C.sub.15 H.sub.21 O.sub.5 PS, 
##STR3## 
C,52.3; H,6.1; S,9.3; P,9.0. Found: C,52.7; H, 6.0; S,9.6; P,9.2. 
The infrared spectrum had a strong absorption band at 3300 cm.sup.-1 
characteristic for --C--OH, and a moderately strong absorption band at 
1030 cm.sup.-1, characteristic of the 
##STR4## 
stretching frequency. There were only very weak absorptions at 1325 
cm.sup.-1 for P.dbd.O, and 980-1080 cm.sup.-1 for covalent --CH.sub.2 
O--P.dbd.O, showing there had been little, if any, oxidation of 
phosphorus. 
EXAMPLES II-XII 
Table I lists the results from reacting various mole ratios of mercaptans 
with triallyl phosphite and triallyl phosphate. Reaction conditions were 
identical with Example I. 
TABLE I 
______________________________________ 
Ex- O.sub.2 Wt. of 
ample RSH absorbed, 
Time Product 
Yield 
No. R.dbd. Moles lbs. hrs. grams Mole % 
______________________________________ 
Triallyl Phosphite 
Reaction Conditions: Reaction Products: 
II C.sub.6 H.sub.5 
0.2 9 24 46.9 97 
III C.sub.6 H.sub.5 
0.3 13.5 72 59 94 
IV n-C.sub.8 H.sub.17 
0.1 6 24 36.8 97 
V " 0.2 10 36 52.6 94 
VI " 0.3 13.8 48 72.9 99 
Triallyl Phosphate 
Reaction Conditions: Reaction Products: 
VII C.sub.6 H.sub.5 
0.1 5 15 34.3 95 
VIII " 0.2 11 25 44.6 89 
IX " 0.3 15 72 62.2 97 
X n-C.sub.8 H.sub.17 
0.1 5 48 36.1 91 
XI " 0.2 11 90 51.4 90 
XII " 0.3 14.8 96 65.6 87 
______________________________________ 
Table II gives the elemental analyses of products of Examples II-XII. 
TABLE II 
__________________________________________________________________________ 
Product of 
Emperical 
Calcd. Found 
Example # 
Formula C H P S C H P S 
__________________________________________________________________________ 
II C.sub.21 H.sub.27 O.sub.7 PS.sub.2 
51.9 
5.6 
6.4 
13.2 
52.6 
5.7 
6.1 
13.8 
III C.sub.27 H.sub.33 O.sub.9 PS.sub.3 
51.6 
5.3 
4.9 
15.3 
50.1 
5.7 
5.0 
15.2 
IV C.sub.17 H.sub.33 O.sub.5 PS 
53.7 
8.7 
8.2 
8.4 
53.0 
8.9 
7.7 
7.9 
V C.sub.25 H.sub.51 O.sub.7 PS.sub.2 
53.8 
9.1 
5.6 
11.5 
54.2 
9.4 
5.7 
11.8 
VI C.sub.33 H.sub.69 O.sub.9 PS.sub.3 
53.8 
9.4 
4.2 
13.0 
54.7 
9.7 
4.8 
12.7 
VII C.sub.15 H.sub.21 O.sub.6 PS 
50.0 
5.8 
8.6 
8.9 
49.7 
5.9 
8.4 
9.1 
VIII C.sub.21 H.sub.27 O.sub.8 PS.sub.2 
50.2 
5.4 
6.2 
12.7 
50.7 
5.8 
6.1 
13.1 
IX C.sub.27 H.sub.33 O.sub.10 PS.sub.3 
50.3 
5.1 
4.8 
14.9 
50.7 
5.6 
4.3 
15.1 
X C.sub.17 H.sub.33 O.sub.6 PS 
51.5 
8.3 
7.8 
8.1 
50.9 
8.6 
8.5 
8.4 
XI C.sub.25 H.sub.51 O.sub.8 PS.sub.2 
52.3 
8.9 
5.4 
11.1 
52.6 
9.4 
5.7 
11.5 
XII C.sub.33 H.sub.69 O.sub.10 PS.sub.3 
52.7 
9.2 
4.1 
12.8 
52.6 
9.6 
4.4 
13.1 
__________________________________________________________________________ 
The products were dark yellow to brown viscous oils. All showed the --C--OH 
band at 3300 cm.sup.-1 and the --S.dbd.O band at 1030 cm.sup.-1 in the 
infrared spectra. The absorption of the products from Examples II-VI 
showed weak absorption at 1325 cm.sup.-1 and 980-1080 cm.sup.-1 for 
P.dbd.O and CH.sub.2 O--P.dbd.O, respectively. In contrast, the products 
of Examples VII-XII had very strong absorption at 1325 cm.sup.-1 and 
980-1080 cm.sup.-1. 
EXAMPLE XIII 
Interfacial tension of compounds of Examples I to XII were determined at 1 
(wt)% concentration between solvent-extracted 5W oil and water, using a 
Cenco-Du Nouy Interfacial Tensiometer No. 70545 with a 6 cm 
platinum-iridium ring at 25.degree. C. with a double distilled water, with 
these results: 
______________________________________ 
Interfacial Tension, 
Product of Example # 
dynes/cm 
______________________________________ 
Control 41.73 
I 8.74 
II 8.46 
III 9.39 
IV 9.30 
V 7.28 
VI 9.30 
VII 18.81 
VIII 16.88 
IX 6.95 
X 4.20 
XI 11.09 
XII 16.30 
______________________________________ 
In the phosphite series Examples I-VI there was little variation in 
surfactant properties, whereas in the phosphate series, Examples VII-XII, 
increasing the mole ratio of phenylsulfoxide content increased surface 
activity, and increasing octyl sulfoxide content decreased surface 
activity. 
EXAMPLE XIV 
Compounds of Examples I to XII were tested in the vial test as cosurfactant 
for enhanced oil recovery, using 5% petroleum sulfonate as surfactant in 
0.8N brine (NaCl), adding the cosurfactant to surfactant at a ratio of 
1:20, and noting the stability of the mixture, as brine tends to cause the 
surfactant to separate (salt) out. The brine-surfactant-cosurfactant 
mixture, 20 ml, was then mixed by shaking with 2.5 ml of crude petroleum 
and the interfacial tension (IFT) observed. Low IFT was indicated by easy 
mixing of the two phases with no separation. Formation of round oil 
droplets that separate quickly indicates a high, ineffective IFT. 
Products of Examples I through VI and IX, X and XI proved effective in 
lowering the IFT in the vial test, giving mixtures of 
brine-surfactant-cosurfactant fluids which were stable, did not separate, 
and easily formed mixtures of the fluid with crude petroleum. Products of 
Examples VII, VIII and XII were poor. 
EXAMPLE XV 
Control of microorganisms in inhibiting or preventing growth of fungi in 
enhanced oil recovery operations is a desirable characteristic of useful 
additives. 
The products of this invention was tested as biocides and inhibitors for 
the growth of microorganisms by this test: 25 g of agar preparation were 
placed in standard Petri dishes. The agar preparation consisted of 23.5 g 
of Bacto Plate Count Agar, Difco Laboratories, Detroit, Mich., dissolved 
in 1 liter of water. Plate Count Agar contains a standard USP formula for 
nutrient agar, consisting of 
5 g: Pancreatic digest of casein 
2.5 g: Yeast extract 
1 g: Glucose 
15 g: Agar 
Four petri dishes were untreated and used as blanks. To the others, in 
duplicate, were added 2.5 ml of 1% acetone solutions of the products of 
Examples I-XII. All plates were uncovered for 4 hours to expose them to 
the spores of adventitious fungi and bacteria, then covered and stored at 
30.degree. C. for 6 days. Ratings were given at this point; 0 represents 
no growth, 5 shows luxuriant colonies of fungi and bacteria. Results were 
as follows: 
______________________________________ 
Product of Example No. 
Rating 
______________________________________ 
I 0,0 
II 0,0 
III 0,0 
IV 0,0 
V 0,0 
VI 0,0 
VII 0,0 
VIII 2,1 
IX 0,0 
X 3,2 
XI 0,0 
XII 0,0 
Control 5,5,5,5 
______________________________________ 
The products of this invention as EP additives, surfactants, and biocides, 
can be used in solutions and formulations at concentrations of 0.001% to 
10% by weight. 
EXAMPLE IX 
A micellar slug for micellar flooding consisting of 3 (vol)% petroleum 
sulfonate as surfactant, 2 (vol)% petroleum hydrocarbon, 1 (vol)% 
cosurfactant comprising a phosphate of a beta-hydroxyethylsulfoxide 
prepared from triallyl phosphate and thiophenol, molecular weight 644, in 
a 1.0N NaCl brine solution is prepared. The micellar slug fluid is fed 
into the high pressure injection pump and is injected into a 25 foot 
section sandstone formation in Crawford County, Ill., USA, through an 
injection well at 900 psig. The amount of slug injected is about 7% of 
reservoir pore volume and the petroleum hydrocarbon is lease crude oil. 
Pattern of injection is two rows of injection wells and three rows of 
producer wells. There are nine wells in each row and total area enclosed 
is 40 acres. Injection and production wells are 460 feet apart and 
adjacent walls are 115 feet apart. Crude oil production increases to 
recover about 30% of the oil in place at start of the injection.