Note: Descriptions are shown in the official language in which they were submitted.
Case 4242/4242-A
Canada
~0'75~53
This invention relates to the use of surfactant salts
to enhance the recovery of oil from oil bearing ~eologic
formations. More particularly the invention includes new
compounds which can be added to aqueous solutions for use
in injecting into appropriate formations for the purpose of
releasing entrapped petroleum materials. The new materials
of the present invention, in aqueous systems having disolved
salt and alk~aline earth metal ions, exhibits improved
stability against hydrolysis at elevated temperatures and for
prolonged periods.
Description of the Prior Art
It is known to use surfactant components added to
aqueous solutions to be used for injection into oil-bearing
formations for the purpose of aiding recovery of petroleum
portions. One, two or three surfactant materials can be used,
singly or in combination. Such prior art is represented, for
example, by U. S. Patents 3,308,068;3,508,612; 3,527,301;
3,714,062; 3,777,818; 3,782,472; and 3,;327,497; and the
references cited therein.` It is evident from the foregoing
typical art that an extremely wide variety of surfactant and
auxiliary materials is known, it also being know that the
effectiveness and longevity of various materials depend upon
numerous factors such a temperature, and the fortuitous or
planned presence or absence of salt and of metal ions contri-
buted by the formation, or otherwise.
~7~3
The composition~ disclo3ed in U. S. Patent 3,827,497
have limitations ln regard to temperature sinc~ they ara ba ed
on or include th~ ~alt~ of sulfated oxyal~ylated al~ohol. 5alt~
which contain the C-()-S llnkage ~re known to be hydrolytically
wlstable ~t elevated temperature~. Sulfonat~s of 3,827,497 are
ethyl sulfonat~3 which are difficult to produce.
Summary of -the Invention
In accordance with the teachlngs of the pre~nt
invent~on, improved surfactant ~alt compo~itions, aqueou~
compo~ition~ of such sal~s, and methods of using such in oil
recov~ry are disclosed. Salts of ~ulfate~ oxyalkyla~ed alcohol
are avoided. By the u~e o~ the propio~ulfonate ~alts of the
present appllcation, compositlons are provided which are ea~ily
produced and whlch inherently have improved hydrolytic stabillty
at elevate~ temperatures, e~pecially in comparison to ~ulfated
ethoxylated alcohols. As a re~ult the presen~ compo31tion~
are re~lstant to hydrolysi~ during the prolonged time the oil
recovery surfactant compositions are r~quired to be in the
ground ln contact with brine and alkaline earth metal ion~.
This property ~s of particular value in Qituatlons where the
oil-bearing formations are located comparatlvely deep within
the earth' 8 aru~t.
Although u~eful $n other ways, the compo3itions of ~he
pre~ent invention are e~peclally useful in ternary combination
2S wlth polyalkyl~ne ylycol alkyl ethers and a ~urfactant ~alt oF
- an organic ~ulfonate such as those descrlbed in U. S. Patent
: . 3,827,497. On the other hand, the surfactant compo~itions are
; characte~ized by being u~eful in aqueous solution~ in general
and of having utillty per se, ~spe~lally for purposes of making
aqueou~ ~olution~.
-2-
r~
:~75~i3
Compos~tions in accordance with the pxesent invantion are
~ropio8ulfonate 3alt5 of the formula RO(C~I2CE~2O)nCI~2C~I2CH2SO3M,
where R i~ alkyl having from about 14 to about 24 carbon atom~,
n 1~ from a~out 2 to about 10, and M i~ ~elected from the group
con~i~kiny of alkali m~tal, amine and ~m~lonium. Preferably
R ha~ from about 16 to about 20 carbon atom~. Preferably n i~
from 3 to about 5. Preferably M i~ ~odium. Preferably th~
16-l~H33-37(C~I2C~2) 3c~l2cH2cH2so3Na.
The foregoing salt compositions are in g~neral u6ed in
aqueous media 30 ~hat other preferre~ compositions are aqueous
~olution~ of the foregoing proplo~ulfonate 9alt3.
Th~ present invention al~o is directecl to an improved
process for recovering oil from a ~ubterranean oil-bearing
format~on whereln the improvement oonsi~t~ in u~ing the foregoing
propiosulfonate salt~.
In another aspect, the present invention relate~ to a
: method of recoverlng oil from a ~ubterranean oil-beaxing
formation whicll comprises A - injecting into the Pormation a
~aline solution containiny a mixture of the followlng components:
: 20 (a) from O.S to 15 percent by welght based on said ~olution of
a surfactant salt of an organic ~ulfonate/ ~b) from 0.25 to 10
percent by weight ba~ed on ~aid solution of a polyalkyl~ne glycol
alkyl ether, and (c) from 0.25 to 10 percent by weight based on
~aid solution of a ~alt of the formula RO~CE12CH2O)nC112CH2CH~$O3M
~5 wherein R i9 alkyl having rom about 14 to about 24 carbon
atom3, n is from about 2 to about 10, and M i.s ~elected from the
group con~i3ting of alkali metal, amine and ammonium an~
B - flooding the ~ormation with a saline solution to effect
oil recovery ther~from. Preferabl~, Component a is an alkali
metal ~al~ of a petroleum sulfonatQ, Component b i~ diethyl~ne
, , , ~ , - - -, ; ,, 1 ~. .. . . . . .. . . . ...
~ .()'7S~3
glycol hexyl ether and Component G ~ ~ an alkali metal ~alt.
Preferably, th~ ~mounts of Component~ a, b and c axe, re~pectively,
2-10 pexc~nt, 1 8 percent and 1-8 percent by weigllt. Preferably,
Component a is an alkali metal salt of a petroleum ~ulfonnt~,
~omponent b i~ a d~ethylene glycol hexyl ether and Component a
ls an alkali metal salt, the amount~ of ComponQnts a, b and c,
rcspectlv~ly, belng 2-10 percent, 1-8 percent and 1~8 percent
b~ welght. Preferably, the ~allne solu~ion in Step ~ cont2ins a
polymer to improve the mobility th~reof, ~uch polymer pre~rably
~lny a poly~accharide.
The composition~ of the pre~ent process can be u~ed in
combin~tion with ~alt~ of 6ulfatQd oxyalkylated alcohol or
~ulfonate~ thereof, such a~ tho~e described in U. S. P~ent
~J827~497r a~ an extender. Thus, ln some ~nstances lt may be
de~ired to inclu~e sulfa ed oxyalkylated alcohol salt in the
pre~ent composition~ with the expectation that, as the ~urfactant
salt containing system progresse~ ~hrough the form~t~on b~coming
mor~ dilute due to the combination wi~h water or bxine pr~en~
in the formation it~elf, a progre~qlve timewise deterioratlon
: 20 o~ ~he le.~ sta~le ~alt of ~ulfated oxyalkylated alcohol can
produc~ a pr~ferred overall process, especially in the presence
of certain alkali metal ion~ such a~ calcium or magne~ium ions.
~rle~ Description of the Vrawln~
.- The figure~ of the drawlng show ~tabill~y charact~r-
i~tic~ for various compo~itlon~ embodylng ~he feature~ o~ th~
. present invention a3 w~ll as for compara~ive compo.~ition~ to
~how th~ superlority of the present compo~ition~ over prior ar~,
Flg. 1 how~ the ~tability charactQri~tic6 o compo~i-
tion~ u~lizing the salt C16_1~H33~37~E)3(C~2)3 3
~0 Fig~ ~ ~how~ the ~tabllity propertle~ of the salt
of Fig. 1 at the temperatur~ o~ ~50F.
!
~'75~S3
E'lg. 3 8hOWB ~che ~tability prop~3rtles of the salt
20+}~4l+o (E~) S (C~l2) 3S03Na at 75F.
FigO 4 show~ the stabllity properties of ~he composi-
tion of Flg. 3 at 150~.
S Fi~. S shows unsati~factory st~bility properti~s o~
a comparative ~alt C20~H41~0 ~E0) 5 (CH2) 2S 3
Fig. 6 ~how~ the ~olubill~y properties of the salt
of Fig. 5 a~ 150F~
Fi~. 7 ~hows the stabllity properti.es of th~ salt
C20~l41+ (E0) 15 (C~I2) 3S03Na at 7SF,
Fig. 8 shows the properties of the ~alt of Fig. 7
at 150 F .
Figs. 9-14 show the stabil.lty properties of the
~alt of ~ig. 1 at 75F and 150F with ~hree addi~ional
petroleum ~ulfonate3.
Description of the Pr ferred Emb di!nents
The pre~rred propio6ul~nate ~ur~ac~an~ ~alts of the
present invention ar~ represented by the formula
RO(C~12C~l2O)nC~2C~2CH2S03M where~n R is alkyl havlng Pxom about
20 lq to about 24 carbon atoms, n is from about 2 to about 10,
and M i~ ~elected from ~he group consi3~ng of alkali metal,
amin0 and ammonium. I~ ~ s notewor~ly that this composition
contains only C-C llnkages, C-0-C linka~es and C-S-0 linkElge~
ln the undamental ~keleton ther~of. Notably ab~ent frorn
- 25 th~e composition6 are the ]cnown unstable ester linkage C-0-C
and the C-O-S linkage of sul~ated oxyalkylated ~lcohol. I~
seen thare~ore that the cvmpositions of the pre~ent invention
~re ¢haracteri~ed by the ab~3enc~3 oE the usual llnkage~ known to
be hydxolytically unstabl! at elevated ~emperature~ and by the
30 presence ln the molecule o~ the prcpiosulfonate group
.
.. . . .. . . . . ..
~S~L53
-CH2~2CH2SO3M. An outstandin~ adv~ntage of ~uch structure6
1~ tha~ the term~ n~l group -C112Cli2CH~S03M can be provi~ed by the
reaction of an oxyalkylat~d alcohol with propane sultone, a
re~ctlon which proceeds readily under comparativ~ly ~imple
condi~ion~ a~ de~crihed in further d~t~l hereinafter.
In general, the ~alt~ o~ the pr~ent lnvention ar~ us~d
in ~ u~e~ olution~ so as to facilitate the introduction
th~reof lnto oil bearing format.ions in the earth. Typical
solutions contain from about 0.005 w~. percen~ to a~out a
~aturation amount of the preferred ~alt in wat~r howeve.r, these
concen-tratlons may ~ary depending upon the method chosen for
making the ~olution and lntroducin~ them into the formation.
Solutions may be intro~uced ~nto the ~ormation separately for
each individual solute or in combinations ~uch a~ with ~urfactant
15 8alt8 of organic sulfonates and o pol~alkylen~ glycol alkyl
ether~, Ruch ternary SyBtemS ln water fre~u¢ntly b~in~
especially pre~erred ~or in~ection. Such 6ystems can be used
with more or less pu~e water or with water which contains
al~ali ~etal halide such a~ sodium chloride in ~olution; vix,
brine, a~ well as with water containing alkaline ~arth metal
ion~, either with ~r without th2 alkali metal halide of the
brine. A prefe~red proces~ then in accordance with the pr~sent
inv~ntion involve~ th~ re~overy of oil from a subterranean
oil-bearing formation by in~cting into the formation a ~aline
~olution ~on~alning the propio8ulf~nat2 0alt of the present
invention, a ~urfactant salt o~ an organic sulfonate and ~
polyalkylene qlycol alkyl ether and tllen ~looding the formation
with an aqueous medium t~ ~~ect oil reco~ry ther~rom. Pre-
fcrr~d flood~ng aqueous medium i5 ~r~qu~ntly ~ brine or sallne
~olution to minimize C08t~ i~her~n~ in ob~aining non~salin~
a~ueou~ ~olutionæ in the field.
-6-
~C~7~53
~ 'I'~le or~ani.c s-llfona~e coml)on~llt~ u~eful .in connectlor
wlth the pr~sent lnvention are typlcally a~ de~crlbed in
U. S. P~ten~ 3,~27,~97~ however, pre~crably tho~ havlng the
un~t~bla struc~ure~ ~Ire avoided where utmo~t ~tabflity o~ the
over2].1 6y~tem i~ de~ir~d. Prcferably, sulfonnt~ ar~ used
which ~re r~adily ~vailabl~ comnlorclally such a~ "~ryton
Ch~mical F467", "Witco Chemical T~S-lO~o Suitabl~ sulfonate~
are usually an~ preferably metal ~alts o~ al}iaryl sulfollate~,
pr~erab].y alkali metal ~alts and alkyl benzenc 3ul0nate3
10 containin~ 12 to 30 carbon ~tom~. 5uitnble ~ulfonates also
can be aliphatic sulfonates, alkylated naphthalene sulfonates
and the like, the essential requirement belng that th~y ha~
surfactant propertie~ The cationic portion of such sulfonates
cnn be ammonium or amine a~ w~ s al~ali metal but is usually
and preferably sodium. The molecular weight of the organic
sulfonate ~urfactant is uRually ln the range of 300-600,
preferably 350-525. These material~ can be prepared by w~ll
known procedures such as those described ln U. S. Patent
3,308,068. They can be prepared synthetically or can be
prepared from.petrole~n and commonly known as petrole~n sul~o-
nates.
The polyalkylene glycol monoalkyl etilers are ~i~ely
available commerclally. The alkylene group is usually ethylene
but can be propylene or others up to about five carbon atom~.
~5 It can repea~ it~elf up to about 10 times (i.eO the "poly" can
be up to about 10~ but usually repeats ltself ~-6 time~, more
usually twice, e.g. diethylene~ It should also be under3tood
thst for any ~pecified polyalkylene, the number of alkyl~ne
unit~ i8 either ~xactly as ~pecified or varle~ but the average
i~ a~ ~p~cifle~ Thls ~ame princlple applie~ al~o to the
-7-
'
~5A~53
alkyl ~roup. Pr~erably the glycol portion i~ diethylenQ glycol.
The al~yl ~roup will normally contain ~-12 carbon atom~, prefer-
ably 4-10. In general the more ~lk~l~ne units or the lon~er the
alk~lene unit, the lon~er the alkyl ~roup should be. The
preferr~d comporlent is ~ie~hylene glycol hexyl ether. Th~se
material~ are nvallable commercially or can be made by known
proc~dure~.
It is evid0nt from the foregoing that the preE~rr~d
compositions in accordance with the pres~nt inventioA are those
cha~acterized by a propiosulfonate structur~ and a preferred
alkoxylated alcohol structure. Such materials typically ara
readily prepared by the reaction o~ alkoxylatcd alcohol~ with
propane 3ul~0ne. This introduc~s the prop~oqulfonate struckure
readily and a~ good yields. Such proces~ preferably utilizes
lS ethoxylated alcohols of the formula RO(CE32CII20)n~l where n 1~
~rom about 2 to ~bout 10 produced by reactin~ alcohol RO}I with
ethylene oxid~. The alcohol ~o reacted may be an aliphatic
alcohol having from about 8 to about 30 carbon atoms per
molecule with a range of ~rom about 14 to about 24 carbon atoms
being especially E~eferred. Pre~erably, the alcohol used is
predominantly a primary alkanol, preerably a synth~tic primary
alcohol mlxture containing up to about 50 ~ercent of branched
primary alcohols. Oth~r ~lcoholic ma~erials can be used ~uch
a~ alkyl phenols cont~inlng ~rom about 5 to about 20 carbon atoms
- 25 p~r alkyl group and the likei Al~hough ethylene oxide i~
preferabl~ reacted with the alcohol in the ratio of from about
2 to a~out 10 molecules of ethylene oxide per molecule o
alcohol, oth~r lower alkylent oxides containing from 2 to abou~
6 carbon atoms axe ~uitable; for example, propylene oxide or
butylene oxide. Typic~l alkoxylated alcohols u~eful in the
!
5~53
present invention rnay incl~lcle substituents such as hydroxy:L or
amine groups anct the lil<e on either the alcohol moiety or the
oxyalkyl portion.
I`he compositions of the present inven-tion provide stable
emulsions in various ways. As an example, an aqueous system
cOntaining lO wt. percen-t Cl6_l8~133_37(E)3( 2)3 3
wi-th 1-l/2 wt. percent NaCl added, 2 cc of C6H130(E0)2~l added
and 20 percen-t by volume of crude oil added was stable.
Propiosulfonates prepared as described in the following
examples and comparative samples were tested using the
following procedure.
To a 4-ounce bottle was added 2.5 grams of petroleum
sulfonate (Petronate~ L of Witco Chemical Company) which is a
petroleum sulfona-te of 415 to 430 equivalent weight range.
Then 1 gram of hexanol ethoxylate averaging two ethoxy
groups per molecule was added.
Next, 1.5 grams (ac-tive basis) of candidate propio-
sulfonate composition or comparative material was added prefer-
ably as an aqueous solution of 10-40 percent concentration, or
as lO0 percent active material.
Next the appropriate amount of sodium chloride was
added preferably as a lO percent aqueous solution to give the
desired final concentration of salt (brine).
Similarly, the appropriate amoun-t of calcium ion was
added preferably as a 1 per cent solution of calcium ion prepared
as calcium chloride.
The sample was then adjus-ted to lO0 grams to provide
the desired concentration of the ingredients. The sample was
then heated and stirred vigorously in a scaled sys-tem to
prevent evaporation of any of the components and when dispersion
::
~'7591~j3
or dissolution wa~ complete the ~amples were placed in an
environment o~ the de~ired temperaturs and observed after
24 hours or mo~e. Ob~xvations were ma~e a~ to the.~stability
or in~tability of the ~y~tem. In~tability in general i8 a
defillite and ea~lly vislble pha~e ~eparation 80 that a curd
of watex-in~oluble material s~parate~ eithQr at the bottom or
the top depending on the brlne concentration6. Generally, all
~olutions are opaqu~. ~ati~factory condltions are stable
di~p~rsions. Rarely, clear ~y~tems are obtained and indicated
by "C". Those which showed good result~ were te~ted further ~
by dllution w~th the appropriate ~odium chloride and calcium ion
solutions at proportions of 1~ 2, 1:5 and 1:10, and
reexamined at the indicated temperatures for stability or
in~tability. Samples w~re tested with 1, 2, 3, 4 and 5 percent
by weight of sodium ahloride and with 200, 500, 1000 and 2000
part~ per million of calcium ion. Data are shown o~ the
Figure~ for the various con~ent~ o~ ~odium chloride, calcium
ion and fox ~he various dilutlons of 0, 1:1 with bxin~ and
calcium ion ~olution, 1:2 with brine and calcium lon ~olutlon,
etc.
The following example~ indlcat~ preferred embod.iments
and a~pects of the present invention.
EX~MPLE I
16-l8H33-37o(c~cH2o)3(cH2~3so3Na
To a 12-liter round bot~om fla~k equipped w~th an
agltator and an off-ga~ trap was charged 1312 gram~ o
C16-18~33_37(~2C~12)3~1 a~exaging three ethoxy units per
molecule. The average molecular weight of ~he alcohol prior to
ethoxylatlon wa~ 260Ø To the fla~k wa~ also added 421 grams
o~ sodium bicarbonate and 2 liter~ of xylene, the latter being
: added ~o a~eotrope water.
- 10~
r
~07S~L53
The fla~k was heated ~o 120D~ and ~e~d of propane
~ultone ~tarted. 435 cc o propane sultone. wa~ Added o~r a
3 hour period, the reaction tempera~ur~ beiny held at about
1~0-14SC.
Agitatlon wa~ cont~nued at a temperatur~ of
144-145C for an a~di~lonal ~ 2 hours. Th~ heat wa~ then
turned off, ~he flask content~ diluted with 5.~ ers of w~te.r,
and the content~ of the fla~k ~tirred for 1-1/2 days.
The cont~nt~ of the flask wer~ then stripped by pa~slng
in nitrog~n at from 0.72 to 0~19 liters p~r minut~ for about
1 hour.
A va~uum was then appl~d, a vacuum of 15 to 18
milllm~ters o mercury being maintained for about 2 llours.
'rhe heat was turn~d of ~t ~bout th~ midpoint of th~ two hours
vacuum treating perio~.
The product waR then d~luted ~o 26 wt. percent product
ln wAter.
The resulting C16_1a propio~ulfona~e was tl~n tested
a~ d~3cri~ed. Data are pres~nted in Figs. 1 and 2 ~or 75~
and 150~F, r~spec~lvely.
EXAMPLE II
C2o~H4l~o(c~2c~l2o~5~cE~2~3so3Na
g C2~l4~ H2C~2O)5~, containing 2S perc~n~
hydrocarbon, -OH ~alue (wt. percent~ 2.17, average m~lecul~r
w~ight 783 (126 millimol~) was charg~d ~o a l-liter fla~k
equippe~ with a magneti~ stlrr~r.
27 grams ~221 mill~mol~) of propane sultone was
-; add~d.
18.7 grams ~2~1 milli~ols) of sodium bicarbonat~ was
add~.
.: .
r
.
~)'7545;~
The mixture was ~tlrred overnight at 130C.
The crud~ product wa~ di~solved ln a mlx-ture o~ 500 ml
~2 and 500 ml m~thyl ethyl ketonQ and extracted three times
with 150 ml portions of a 2:1 volume mixture of m~thyl ethyl
ketone and h~xan~ (lO0 ml m~thyl ethyl keton~ + 50 ml hex~ne).
Th~ mixture wa~ heated to ~eparate the phase~.
The aqueou~ phase was evaporatod overnight on a
hot plate to dryneR~ giving 64 grams of crude product.
The crude product wa~ desalted with 1600 ml of 50
percent aqueous isopropanol and 224 grams Na2CO3. The solvent
was evaporated and product ~ried in oven ov~rn~ght. The product
was anal~z~d by in~rared and wat chemical analy~is and found to
be con~ist~nt for the produc~.
The resulting C20 propiosul~onate wa~ then tested
a~ de~cribed. ~ata are pre~ented ln Figs. 3 and 4 for 7S~F
and 150F, respectively.
EXAMPLE III
C20~1141+ (Cl'l~CH2) 5cH2cl~2so3Na
70 7 gram~ (90.3 millimol~) of the C20~H22+Ol 2 ~ 5
e~lo~ylated alcohol of Example II was placed in a flask and
heat~d with lB.0 grams (77.4 millimol~ oE sodium methoxide
a~ a 24 percent Rolution in methanol wl~h ~tirring ~or 1.5
: hou~s at 130C and 200 mm~pres~ure. Thi~ produ¢es th~ ethoxy
al~ohol alkoxlde.
17,7 grams (77~4 mllllmols) of bromoe~hane sulfonate
~BrC~2CH~SO3Na~ in water wa~ azeotroped with toluene to remove
; ~he water.
The ethoxy alcohol alkoxide wa~ then added to the
bromoethane Hulonate. About 40 ml undecane w~ added to
facilitate ~tir.ring and the mixture waR. heated to 200C and
~tirred fox 3 hours.
-12-
~ ~ r - ~
~75~5;3
~he reaction mixture wa6 cooled to roorn temperature
and disqolved in 700 ml of 50 percent aqueous methyl ethyl
lsetone and ~xtracted twice with 200 ml portions of ~:1 rnethyl
ethyl ketone ~ hexane .
The aqueou~ solutlon wa~ evaporate~l to about 150 ml
~nd then d~altecl with 900 ml of 50 parc~nt aqueous i.~opropanol
and 126 gram~ of Na2C03. The ~ystem was then evaporated
overnight to dryn~s in a 120 ov~n.
The resultlng C20~ ~2thyl sulfonate wa~ then te~ted
10 a~; described. Data are presentec3 in Figs. 5 and 6 for 75F and
150F, xe~pectiYely and ara ~een to be inferior to the
propio~ulfonate~ of Figs. l-g~
EX~PLE IV
C20~H41+~c~2c~l20)15(c~I2)3so3~a
; 15 g C20+H41+(CH2~H2)15~l/ co~tainlng 15 per-
cent by hydrocarbon, -OH value (wt. percent) 1.39, average
molecular weight 1223 (81 millimols) wa~ charged to a l~liter
fla~k equipped with a magnetic ~tirrer. To the fla~k was added
14. 8 gram~ ~122 millimols) of propan~ sulton~ and 10 . 3 ~rams
~122 millimols) of sodium bicarbonate.
The mixture was ~tirred for 8 houxs at 135C and
allowed to stand overnight. Product work-up was a~ descri~ed in
~ Example II.
- Th~ resulting product wa~ te~ted as described. O~ta
25 are presented in Figs. 7 and 8 for 75F and 150F, re~pectilrely.
Re~ult~ with a propiosulfonate hav~ ng 15 ~thylene oxi~le units
per molecule are shown to be inferior to those with the propio-
sulfonate~ of Fig~ 4.
~rom the oregolng, it 18 evidenl: that the featur~
30 of the present invention may b~ employed in various ways.
-13-
. ~75g~i3
~ltl~ough khe ~'20~ an~l Clfi_l~ 0~1t coln~o~ition~ ~r~ pr~crre-l
mlx1:ure~3~ lndlvlllu~l l3alt; ~uch ~ tho~ w~lereln th~ nlhyl
grouI~ ha~ 16, l~, ~0, 22, ~to. carbon atom~ m~y bQ n~ed.
I~XA~IPJ.l`~,~ V~VII
C16-lU~133~37 (C~2C~1~0) 3 (C~l~) 3~;031~a
IqlG AbOV~ prOpl08UlfOll~tQ nEI UElUtl ln ExuLm~ I w~
te~ted wlth ~i~feront p~trol~ ulfonate6 ~lth (1~ ~er~nt
proportlonL~ .
For each of 1:h~ followin~ eX2111ple~, ln~te~d o~
- 10 2.5 ~rams o~ tho petrole~lm ~ulfonnto, 3.0 grarn wa~ used~ A8
be~ore, one gram o~ thQ hexanol ethoxylut~ ~vera~lrlg two
ethoxy qxoup~ p~r molecul~} was u~ed. In~t~ad o~ l. 5 gram~
(~ctiv~: bAsi~ o~ candidatQ proplo~ulfonat~, l . 0 gram~ wa~
u~ed. Otherwis~ tha procedur~ d~scrlbed previously w~
followe~ at 1, 3 and 5 percent by wei~ht vf ~odlum chlorld~ and
w~h 200, 500, 10~0 and 2000 par~s per mi11ion of calcium ion,
th~ te~t1n~ ~or th~ non~iluted ~mple of Example ~I (Fi~
~nd 1~ ing extende~ to includ~ 6, 8, 10 and 12 pe~c~nt by
w~ight of sodi-~ chlori~ ancl 5000 and 10,000 ~art~ ~er m~11ion
~f cRlcium ion- to Yhow how far ~tabi1ity extended beyond t~
:~ rsnge~ o~ usual inter~
EX~LE V
Th~ p~tro1~um s~lfon~te used was Petroste~4~0 of
~t~pan Chemic~1 Company ~hich 15 ~ 60 p~rcent activs material
having ~1 percent ~ree o~l, 17.5 percent water, 1.5 percen~
inor~anlc sa1t~ and ~n appro~ima~o equival~nt welght ~f 4200
D~ta ara ~hown for 75~ and 150F by Figs. 9 and 10,
re~pPctively O
.
,
, _, ., . . .. . . . _ _ . ... .. . , _ .. . ..
~.~.. , . ' .
- :
i915~
L~: VI
Tl~ pctrol~lm sul~onatc~ u~d waE3 }~otrOEIt~p 450 o
Stap~n C:hcmical Compnrly ~hlch ~ cl a 60 percc~nt ~ctivC ~at:~x~ al
h~ving 13.5 porc~nt freo oil, 2~.5 percf~nt w~tcr, 2.0 ~cxcent
5 inor~atlic oaJ.ts nntl an approxlmat~ equlvnlent w~lc3ht of ~50.
Data ar~3 showIl or 75~F ~lnd 150F by FicJ~. 11 nnd 12,
ra~pectively .
t~lrL~ VI I
Th~3 petroleum ~ulfon~tc used ~A3 Petrost:er) ~S of
10 StQparl Chemical Co~npany ~"hich 1~ ~ 60 percent: actlve mat~rial
havin~ 13.1 perc~n~ r~e oil, 23 . 5 percent wa~ex, 3. 6 percent
inorganic 8alt5 and an approxlmat~ equlvalent weic3ht o
465. Data arc shown for 75~F and 150F ~y Fig~. 13 ancl 14,
re~pec~tively.
~-lS-
. ~'
:
.... .
~ - ~ . . .
. . . . , , . . ~ , . , ~, . ..
